EP1077245A2 - Inhibitor composition for stabilising radically polymerisable substances - Google Patents

Inhibitor composition for stabilising radically polymerisable substances Download PDF

Info

Publication number
EP1077245A2
EP1077245A2 EP00116293A EP00116293A EP1077245A2 EP 1077245 A2 EP1077245 A2 EP 1077245A2 EP 00116293 A EP00116293 A EP 00116293A EP 00116293 A EP00116293 A EP 00116293A EP 1077245 A2 EP1077245 A2 EP 1077245A2
Authority
EP
European Patent Office
Prior art keywords
inhibitor composition
ppm
inhibitor
oxyl
derivative
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Granted
Application number
EP00116293A
Other languages
German (de)
French (fr)
Other versions
EP1077245A3 (en
EP1077245B1 (en
Inventor
Heinz Friedrich Dr. Sutoris
Gerhard Dr. Wagenblast
Volker Dr. Schliephake
Jürgen Dr. Schröder
Harald Dr. Keller
Thomas Dr. Jaworek
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
BASF SE
Original Assignee
BASF SE
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by BASF SE filed Critical BASF SE
Publication of EP1077245A2 publication Critical patent/EP1077245A2/en
Publication of EP1077245A3 publication Critical patent/EP1077245A3/en
Application granted granted Critical
Publication of EP1077245B1 publication Critical patent/EP1077245B1/en
Anticipated expiration legal-status Critical
Expired - Lifetime legal-status Critical Current

Links

Classifications

    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K15/00—Anti-oxidant compositions; Compositions inhibiting chemical change
    • C09K15/04—Anti-oxidant compositions; Compositions inhibiting chemical change containing organic compounds
    • C09K15/32—Anti-oxidant compositions; Compositions inhibiting chemical change containing organic compounds containing two or more of boron, silicon, phosphorus, selenium, tellurium or a metal
    • C09K15/322—Anti-oxidant compositions; Compositions inhibiting chemical change containing organic compounds containing two or more of boron, silicon, phosphorus, selenium, tellurium or a metal containing only phosphorus
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K15/00—Anti-oxidant compositions; Compositions inhibiting chemical change
    • C09K15/04—Anti-oxidant compositions; Compositions inhibiting chemical change containing organic compounds
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07B—GENERAL METHODS OF ORGANIC CHEMISTRY; APPARATUS THEREFOR
    • C07B63/00—Purification; Separation; Stabilisation; Use of additives
    • C07B63/04—Use of additives
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C51/00—Preparation of carboxylic acids or their salts, halides or anhydrides
    • C07C51/42—Separation; Purification; Stabilisation; Use of additives
    • C07C51/50—Use of additives, e.g. for stabilisation
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C67/00—Preparation of carboxylic acid esters
    • C07C67/48—Separation; Purification; Stabilisation; Use of additives
    • C07C67/62—Use of additives, e.g. for stabilisation
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K15/00—Anti-oxidant compositions; Compositions inhibiting chemical change
    • C09K15/04—Anti-oxidant compositions; Compositions inhibiting chemical change containing organic compounds
    • C09K15/30—Anti-oxidant compositions; Compositions inhibiting chemical change containing organic compounds containing heterocyclic ring with at least one nitrogen atom as ring member

Definitions

  • the invention relates to an inhibitor composition and its use for Stabilization of radical polymerizable substances and a Mixture containing inhibitor composition.
  • radical polymerization Many compounds that have one or more vinylically unsaturated groups have a pronounced tendency towards radical polymerization. Such connections are also used specifically as monomers for radical polymerization. At the same time, however, there is a pronounced tendency towards radical polymerization disadvantageous than it is in both storage and chemical and / or physical processing (e.g. distillation or rectification), especially under the Exposure to heat and / or light, for undesired radical polymerization of vinyl unsaturated compounds can come. An unwanted radical Polymerization can, especially if polymer is deposited, in negative effects in different ways.
  • distillation of vinylically unsaturated compounds formed by radical polymerization Precipitate polymer on the surface of the evaporator used - there it is Radical polymerization tendency particularly strong due to the high temperatures pronounced.
  • Polymerization in the area of the surface of an evaporator means in the Rule that a polymer layer forms on the surface. Due to the insulating effect of the polymer layer, the heat transfer becomes undesirable Way diminished.
  • Polymer undesirably formed by radical polymerization can also block the internals of rectification columns, which is undesirable Pressure loss caused. Polymer deposition can ultimately do that Interrupting the rectification process is necessary, because to continue the Rectification the deposited polymer must be removed.
  • US-A 4,187,382 relates to a process for the esterification of organic diols with Acrylic acid. It is recommended to pretreat the diol with triphenyl phosphite in order to The tendency of the reaction mixture to reduce radical polymerization.
  • As another inhibiting component is a phenolic polymerization inhibitor suggested.
  • DE-A 29 13 218 discloses a process for the preparation of acrylic acid esters or Methacrylic acid esters in which organic phosphites are used as a polymerization inhibitor can be used together with phenolic polymerization inhibitors.
  • the inhibitor compositions mentioned above contain phosphorus compounds which Have phosphorus in the oxidation number +3 and also phenolic compounds.
  • One goal is to have the effect of such systems in stabilizing vinyl to further improve unsaturated compounds.
  • the object of the present invention is a strong-acting To produce inhibitor composition, the phosphorus in the oxidation number +3 contains chemical compounds and / or phenolic compounds. This Inhibitor composition should be effective, the inhibitory effect of the components contained in it should reinforce in a synergistic manner.
  • an inhibitor composition containing as components a) at least one nitroxyl radical (derivative), b) at least one Phenol (derivative) and c) at least one further chemical compound which at least contains a phosphorus atom which has an oxidation number of +3.
  • the oxidation number of an atom within a covalent compound is to be understood as a number with a positive or negative sign, which indicates the charge that the atom would have if the binding electron pairs of the covalent bonds in which the atom takes part is the more electronegative binding partner allocated.
  • Electronegativity is to be seen as a measure of how strongly an atom in a molecule attracts electron pairs that are bound to the atom.
  • the relevant electronegativities are those according to HR Christen, Fundamentals of General and Inorganic Chemistry, Verlag Sauerators, Aarau, Diesterweg-Salle, Frankfurt am Main (1973).
  • orthophosphorous acid or an ester of orthophosphorous acid can be used.
  • Esters of Orthophosphorous acid are also known as phosphites.
  • the orthophosphorous Acid can also be present as a salt (usually as an alkali metal or ammonium salt).
  • Preferred binding partners of the phosphorus are the elements C, S, O, N and / or H.
  • Particularly suitable phosphites that is, the esters of orthophosphorous acid
  • phosphonites esters of phosphonous acid
  • triphenyl phosphite diphenylalkyl phosphite, phenyl dialkyl phosphite, tris (nonylphenyl) phosphite, trilauryl phosphite, trioctadecyl phosphite, distearylphentaerythritol (2,4) butylphenyl) phosphite, diisodecypentaerythritol diphosphite, bis (2,4-di-tert-butylphenyl) pentaerythritol diphosphite, bis (2,6-di-tert-butyl-4-methylphenyl) pentaerythritol diphosphite, diisodecyloxypentaery
  • esters of orthophosphorous acid (phosphites) of the general formula (I) or esters of phosphonous acid (phosphonites) of the general formula (II) used where R, R ', R''may be the same or different and organic radicals in particular C 1 -C 20 alkyl, hydroxy-C 2 -C 4 alkyl, halogen-C 2 -C 4 alkyl, especially chloroalkyl , -C 6 -C 10 aryl, especially phenyl or aryl substituted by C 1 -C 8 alkyl (especially phenyl substituted by C 1 -C 4 alkyl).
  • Two of the three organic radicals R, R ′ and R ′′ together with the phosphorus and the two oxygen atoms can also form a heterocycle (for example 5- or 6-atom).
  • Trimethyl, triethyl, tributyl, trihexyl, trioctyl, triphenyl, tri-p-cresyl, trixylyl, tritolyl and tri- ⁇ -chloroethylphosphite may be mentioned by name.
  • dimethyl, diethyl, dibutyl, dioctyl, diphenyl, ditolyl and dixylyl phosphites are also suitable inhibitors according to the invention.
  • Irgafos® 168 manufactured by Ciba AG
  • Irgafos® P-EPQ manufactured by Ciba AG
  • Ultranox® 626 manufactured by GE-Specialty Chemicals GmbH
  • Suitable nitroxyl radicals come according to the invention in principle all compounds which have at least one> N-O ⁇ - Have group.
  • the nitroxyl radical (derivatives) can also be generated in situ from others Connections are created, e.g. by H abstraction from hydroxylamines or by Addition of C radicals to nitrons. You can also choose from aromatic amines that derived from aniline or phenylenediamine, generated in situ.
  • Nitroxyl radicals which are suitable according to the invention come primarily from those Consider that are derived from a secondary amine that does not contain hydrogen atoms on the ⁇ -C atoms (i.e., the N-oxyl groups derive from corresponding secondary amino groups).
  • suitable compounds are those stable nitroxyl radical (derivatives) of the general formula (IV) in which R 1 , R 2 , R 5 and R 6 represent (same or different) C 1 to C 4 alkyl groups such as methyl -, ethyl, n-propyl, iso-propyl, n-butyl, iso-butyl or tert-butyl, linear or branched pentyl, phenyl or substituted groups thereof and R 3 and R 4 for (Same or different) C 1 - to C 4 -alkyl groups such as methyl, ethyl, n-propyl, iso-propyl, n-butyl, iso-butyl or tert-butyl, linear or branched pentyl -, substituted groups of these or together with CNC for the cyclic structure where n is an integer from 1 to 10 (often 1 to 6), including substituted such cyclic structures.
  • Exemplary representatives include 2,2,6,6-tetramethyl-1-oxyl-piperidine, 2,2,5,5-tetramethyl-1-oxyl-pyrrolidine and 4-oxo-2,2,6,6-tetramethyl- Called 1-oxyl-piperidine.
  • N-oxyl radical (derivatives) of the general form (IV) can be derived from the corresponding secondary amines by oxidation, e.g. with hydrogen peroxide, produce. As a rule, they can be represented as pure substances.
  • N-oxyl radicals suitable according to the invention are 1-oxyl-2,2,6,6-tetramethylpiperidine, 1-oxyl-2,2,6,6-tetramethylpiperidin-4-ol, 1-oxyl-2,2,6,6-tetramethyl-4-methoxypiperidine, 1-oxyl-2,2,6,6-tetramethyl-4-ethoxypiperidine, 1-oxyl-2,2,6,6-tetramethyl-4-trimethylsiloxypiperidine, 1-oxyl-2,2,6,6-tetramethylpiperidin-4-one, 1-oxyl-2,2,6,6-tetramethylpiperidin-4-yl acetate, 1-oxyl-2,2,6,6-tetramethylpiperidin-4-yl-2-ethylhexanoate, 1-oxyl-2,2,6,6-tetramethylpiperidin-4-yl stearate, 1-oxyl-2,2,6,6-tetramethylpiperidin-4-yl benzoate, 1-oxyl-2,2,6,6-te
  • the inhibitor composition contains, as a further component - component b) - at least one phenol (derivative) (phenol as such is also suitable as a phenol derivative).
  • phenol as such is also suitable as a phenol derivative.
  • phenols or cresols in which one or more hydrogen atoms are substituted by i-propyl groups, such as thymol or carvacrol. Pyrocatechol and its derivatives as well as resorcinol and its derivatives are also suitable.
  • hydroquinone and its derivatives are also suitable as dihydric phenols.
  • Naphthols such as ⁇ -naphthol and vitamin E are also suitable.
  • phenols which are connected to one another via alkyl bridges such as bisphenol A.
  • suitable phenol derivatives are compounds which can form an oxyl radical which is bonded to an aromatic system. This is done by homolytic cleavage of an oxygen-hydrogen bond, the oxygen atom being bound to an aromatic system.
  • Particularly preferred phenol derivatives are represented by the following general structural formula (XIII):
  • the inhibitor composition containing one or more chemical compounds which contain at least one phosphorus atom with the oxidation number +3, and one or more nitroxyl radical (derivatives) and one or more phenol (derivatives) has one particularly good stabilizing effect on the effect as an inhibitor in the
  • the inhibitor composition according to the invention exhibits radical polymerization synergistic properties on - species of the three different inhibitor components reinforce each other in their inhibitory effect. Accordingly, the inhibitory Effect of the combination of the invention better than the inhibitory effect that for example if only the individual components were present, or than the addition of the individual effects.
  • the inhibitor composition according to the invention is also effective in Developed in the presence of molecular oxygen.
  • inhibitor compositions In the following, particularly suitable inhibitor compositions will be discussed. Components contained in these inhibitor compositions are listed in the table below - the combination of the following components has proven to be particularly advantageous:
  • the inhibitor system according to the invention In the case of rectification and distillation processes, comparatively less polymer is deposited if the inhibitor system according to the invention is used, so that the corresponding plants have to be shut down less often because of cleaning work. In addition, the synergistic inhibitor system ensures that less monomer is consumed by polymerization and thus get lost".
  • the inhibitor composition in addition to the described inhibitors - Phosphorus compounds, nitroxyl radical (derivatives), phenol (derivatives) - yet another one contain radical polymerization inhibiting components.
  • radical polymerization inhibitors are organic nitroso compounds such as N-nitrosoarylamines.
  • the inhibitor compositions are used to stabilize Pure substances which have at least one vinylically unsaturated group or of Mixtures that contain at least one substance that contains at least one vinyl has unsaturated group used.
  • the inhibitor composition also works in Presence of oxygen.
  • a mixture comprising at least one is also provided Compound which has at least one vinylically unsaturated group and one inhibitor composition according to the invention.
  • the mixture usually contains one or more chemical compounds, which contain at least one phosphorus atom having the oxidation number +3, in one Total concentration from 1 to 5000 ppm, preferably from 5 to 1000 ppm, and one or several nitroxyl radicals (derivatives) in a total concentration of 1 to 3000 ppm, preferably from 5 to 300 ppm and one or more phenol derivatives in one Total concentration from 1 to 3000 ppm, preferably from 5 to 1500 ppm.
  • one or more chemical compounds which contain at least one phosphorus atom having the oxidation number +3, in one Total concentration from 1 to 5000 ppm, preferably from 5 to 1000 ppm, and one or several nitroxyl radicals (derivatives) in a total concentration of 1 to 3000 ppm, preferably from 5 to 300 ppm and one or more phenol derivatives in one Total concentration from 1 to 3000 ppm, preferably from 5 to 1500 ppm.
  • the compounds which have at least one vinylically unsaturated group are to be understood in particular to be those which can be homopolymerized and / or copolymerized by free radicals.
  • examples include olefins such as isobutene, ethylene or propylene, vinyl aromatic monomers such as styrene, ⁇ -methylstyrene, o-chlorostyrene or vinyltoluenes, C 4 -C 8 -conjugated dienes such as butadiene or isoprene, esters from vinyl alcohol and 1 to 18 C- Atomic monocarboxylic acids such as vinyl acetate, vinyl propionate, vinyl n-butyrate, vinyl laurate or vinyl stearate.
  • 3 to 6 carbon atoms are ⁇ , ⁇ -monoethylenically unsaturated mono- and dicarboxylic acids, such as in particular acrylic acid, methacrylic acid, maleic acid, fumaric acid and itaconic acid, the esters of the aforementioned carboxylic acids and 1 to 12, preferably 1 to 4, C- Alkanols containing atoms, such as, in particular, methyl, ethyl, n-butyl, isobutyl, tert-butyl and 2-ethylhexyl acrylate and methacrylic acid; Maleic acid dimethyl ester or maleic acid di-n-butyl ester, is suitable.
  • mono- and dicarboxylic acids such as in particular acrylic acid, methacrylic acid, maleic acid, fumaric acid and itaconic acid, the esters of the aforementioned carboxylic acids and 1 to 12, preferably 1 to 4, C- Alkanols containing atoms, such as, in particular
  • precursor aldehydes, nitriles and amides of the aforementioned 3 to 6 are also suitable ⁇ , ⁇ -monoethylenically unsaturated mono- and dicarboxylic acids containing C atoms, for example acrolein, methacrolein, acrylonitrile, methacrylonitrile, acrylamide and Methacrylamide.
  • Monomers such as vinyl sulfonic acid, vinyl phosphonic acid, N-vinylimidazole and N-vinyl pyrrolidone are also suitable.
  • the inhibitor composition according to the invention is an additive both for storage stabilization as well as for process stabilization (manufacturing, cleaning and chemical conversion) of compounds containing at least one vinylically unsaturated group.
  • the latter also applies in particular to distillative processes that are usually involved Temperatures from 50 to 300 ° C, preferably at 50 to 200 ° C, particularly preferably at 50 up to 150 ° C.
  • the stabilization with the inhibitor composition according to the invention is particularly suitable for the distillative (rectificative) treatment of (meth) acrylic acid esters (in particular the aforementioned exemplary representatives), for their distillative or rectificative separation from product mixtures, such as is the result of an acid-catalyzed esterification of (meth) acrylic acid with alcohols, in particular alkanols (in particular C 1 to C 12 or C 1 to C 8 alkanols) before and / or after removal of the acid catalyst.
  • alcohols in particular alkanols (in particular C 1 to C 12 or C 1 to C 8 alkanols) before and / or after removal of the acid catalyst.
  • the stabilization of one subjected to distillation or rectification Mixture containing (meth) acrylic acid esters can be such that the inhibitors already added to the mixture before distillation.
  • an inhibitor can be added to the top of the column for stabilization respectively.
  • the entire stabilization can only be done by inhibitor is added to the top of the column.
  • the various components of the inhibitor composition according to the invention can added sequentially, simultaneously or even premixed.
  • the the aforementioned also applies to the other inhibitors, if the inhibitor composition is one includes.
  • the addition of the components of the inhibitor composition to different Addition locations are made.
  • components of the Inhibitor systems at the top of the rectification column and other components of the Inhibitor systems in the bottom and / or the inlet of the rectification column become.
  • This applies both to such retifications as part of the (Meth) acrylic acid esters are removed via the top, bottom and / or side draw becomes.
  • It can also be expedient to use the method according to the invention in the case of a continuous distillative (retificative) separation of (meth) acrylic esters perform that at least one inhibitor component to be supplied continuously, but only from time to time, i.e. recurring, is added (e.g. at the top of the column, in the bottom and / or in the feed).
  • (meth) acrylic acid can be obtained by catalytic gas phase oxidation of alkanes, alkanols, alkenes or alkenals which contain 3 or 4 carbon atoms.
  • (Meth) acrylic acid is particularly advantageously obtainable, for example, by catalytic gas phase oxidation of propane, propene, tert-butanol, isobutene, isobutane, isobutyraldehyde or methacrolein.
  • starting compounds are also conceivable from which the actual C 3 - / C 4 starting compound only forms intermediately during the gas phase oxidation.
  • the methyl ether of tert-butanol may be mentioned as an example.
  • These starting gases are usually diluted with inert gases such as nitrogen, CO, CO 2 , saturated hydrocarbons and / or water vapor, in a mixture with oxygen at elevated temperatures (usually 200 to 400 ° C) as well as optionally increased pressure via transition metals (e.g. Mo , V, W and / or Fe) mixed oxide catalysts passed and oxidatively converted into (meth) acrylic acid.
  • inert gases such as nitrogen, CO, CO 2 , saturated hydrocarbons and / or water vapor
  • the dilution phase is not a pure one in catalytic gas phase oxidation (Meth) acrylic acid, but obtained a reaction mixture that essentially (Meth) acrylic acid, which contains inert diluent gases and by-products, from which the (meth) acrylic acid must be separated.
  • reaction gas mixture contains less disruptive by-products such as acetic acid often also closely related to (meth) acrylic acid and therefore difficult for (meth) acrylic acid separable lower aldehydes such as formaldehyde, acetaldehyde, acrolein, methacrolein, Propionaldehyde, n-butyraldehyde, benzaldehyde, furfural and crotonaldehyde as well additionally optionally maleic anhydride (based on that in the reaction gas mixture Containing amount of (meth) acrylic acid is the total amount of this, at Subsequent uses often significantly disruptive, secondary components usually ⁇ 2 % By weight, usually ⁇ 0.05% by weight).
  • secondary components usually ⁇ 2 % By weight, usually ⁇ 0.05% by weight.
  • acrylic acid from the reaction gas mixture of the catalytic Gas phase oxidation of propylene and / or acrolein by countercurrent adsorption a high-boiling inert hydrophobic organic liquid.
  • the Inhibitor composition can be directly in the gas stream or in the device for Countercurrent adsorption are injected.
  • an organic liquid for the Counterflow adsorption comes, among other things, higher alcohols or esters of these (especially those with (meth) acrylic acid) in question.
  • the procedure is essentially performed so that the reaction gas mixture in a conventional Adsorption column leads to the descending adsorption liquid in countercurrent, then in a desorption column from essentially acrylic acid, the Adsorbent and secondary components compound liquid drain Adsorption column by stripping (stripping) with inert gas, the easily separable volatile secondary components largely removed and then the (Meth) acrylic acid and the liquid drain containing the adsorbent as main components the desorption column for the separation of crude acrylic acid treated rectificatively.
  • the invention is Inhibitor composition applicable.
  • the invention Inhibitor composition also in the extraction of (meth) acrylic acid from the Reaction mixture of the gas phase oxidation can be used.
  • the inhibitor composition can be injected directly into the gas stream. Stabilization is recommended also in the case of a crystallized separation of (meth) acrylic acid or its ester containing mixtures.
  • (Meth) acrolein is similar to (meth) acrylic acid e.g. through catalytic Gas phase oxidation available. However, the oxidation occurs after the first Oxidation level discontinued. Rather, it is in the reaction gas mixture Containing (meth) acrolein usually first extractively from the water Separated reaction gas mixture and then by distillation (rectification) from the aqueous solution. Stabilization is suitable for all the process steps mentioned the inhibitor composition according to the invention.
  • the synergistic effectiveness of the inhibitor composition according to the invention applies in essentially independent of the pH value and both for lower (e.g. room temperature) than also for elevated temperatures, as z. B. in the context of thermal physical Separation processes as well as for chemical processes occurring at elevated temperatures Implementations are common.
  • the inhibitor composition is chosen such that the amount of the components contained in the inhibitor composition is completely soluble in the substance to be stabilized. Often they are not added as pure substance, but as a suspension, emulsion or solution. Suitable solvents and / or dispersing media are, in particular, those substances which are part of the system to be stabilized, ie, for example in chemical reactions such as esterifications, all starting materials and products. In the following, the invention will be explained in more detail using an exemplary embodiment.
  • test results show that when all three inhibitor types are used - that is to say compounds which have a phosphorus atom in the oxidation number +3, and nitroxyl radical (derivatives) and phenol (derivatives) - there is a particularly long time before the corresponding sample has solidified .

Landscapes

  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • Polymerisation Methods In General (AREA)
  • Hydrogenated Pyridines (AREA)
  • Compositions Of Macromolecular Compounds (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
  • Treatment Of Sludge (AREA)
  • Anti-Oxidant Or Stabilizer Compositions (AREA)

Abstract

Inhibitor composition contains at least one nitroxyl radical (derivative), at least one phenol (derivative) and at least one other chemical compound containing phosphorus (P) atom(s). Inhibitor composition contains: (a) at least one nitroxyl radical (derivative) (I); (b) at least one phenol (derivative) (II); and (c) at least one other chemical compound (III) containing phosphorus (P) atom(s) with oxidation number +3. An Independent claim is also included for mixtures containing compound(s) with vinyl unsaturated group(s) and the inhibitor composition.

Description

Die Erfindung betrifft eine Inhibitorkomposition, sowie deren Verwendung zur Stabilisierung von radikalisch polymerisierbaren Substanzen und ein die Inhibitorkomposition enthaltendes Gemisch.The invention relates to an inhibitor composition and its use for Stabilization of radical polymerizable substances and a Mixture containing inhibitor composition.

Viele Verbindungen, die ein oder mehrere vinylisch ungesättigte Gruppen aufweisen, haben eine ausgeprägte Neigung zur radikalischen Polymerisation. Solche Verbindungen werden als Monomere für die radikalische Polymerisation auch gezielt eingesetzt. Gleichzeitig ist die ausgeprägte Neigung zur radikalischen Polymerisation aber insofern von Nachteil, als es sowohl bei der Lagerung als auch bei der chemischen und/oder physikalischen Bearbeitung (z.B. Destillation oder Rektifikation), insbesondere unter der Einwirkung von Wärme und/oder Licht, zur unerwünschten radikalischen Polymerisation der vinylisch unge-sättigten Verbindungen kommen kann. Eine unerwünschte radikalische Polymerisation kann, insbesondere falls Polymer abgeschieden wird, sich in unterschiedlicher Weise negativ auswirken. Beispielsweise kann sich bei der Destillation von vinylisch ungesättigten Verbindungen durch radikalische Polymerisation gebildetes Polymer auf der Oberfläche des eingesetzten Verdampfers niederschlagen - dort ist die Neigung zur radikalischen Polymerisation infolge der hohen Temperaturen besonders stark ausgeprägt. Polymerisation im Bereich der Oberfläche eines Verdampfers bedeutet in der Regel, daß sich eine Polymerschicht an der Oberfläche ausbildet. Aufgrund der isolierenden Wirkung der Polymerschicht wird der Wärmeübergang in unerwünschter Weise vermindert. Durch radikalische Polymerisation unerwünscht gebildetes Polymer kann aber auch die Einbauten von Rektifikationskolonnen verstopfen, was unerwünschte Druckverluste verursacht. Die Abscheidung von Polymer kann letztendlich das Unterbrechen des Rektifikationsprozesses erforderlich machen, da zur Fortführung der Rektifikation das abgeschiedene Polymer entfernt werden muß.Many compounds that have one or more vinylically unsaturated groups have a pronounced tendency towards radical polymerization. Such connections are also used specifically as monomers for radical polymerization. At the same time, however, there is a pronounced tendency towards radical polymerization disadvantageous than it is in both storage and chemical and / or physical processing (e.g. distillation or rectification), especially under the Exposure to heat and / or light, for undesired radical polymerization of vinyl unsaturated compounds can come. An unwanted radical Polymerization can, especially if polymer is deposited, in negative effects in different ways. For example, distillation of vinylically unsaturated compounds formed by radical polymerization Precipitate polymer on the surface of the evaporator used - there it is Radical polymerization tendency particularly strong due to the high temperatures pronounced. Polymerization in the area of the surface of an evaporator means in the Rule that a polymer layer forms on the surface. Due to the insulating effect of the polymer layer, the heat transfer becomes undesirable Way diminished. Polymer undesirably formed by radical polymerization can also block the internals of rectification columns, which is undesirable Pressure loss caused. Polymer deposition can ultimately do that Interrupting the rectification process is necessary, because to continue the Rectification the deposited polymer must be removed.

Es ist daher allgemeine Praxis, vinylisch ungesättigten Verbindungen, die radikalisch polymerisierbar sind und Gemischen, die solche Verbindungen enthalten, Verbindungen zuzusetzen, die als Inhibitoren bzw. Retarder der radikalischen Polymerisation fungieren. Während Inhibitoren die radikalische Polymerisation - bis zu deren vollständigen Umsetzung mit freien Radikalen - unterbinden, verlangsamen Retarder die radikalische Polymerisation. Inhibitoren und Retarder werden im allgemeinen unter dem Oberbegriff Stabilisatoren zusammengefaßt. Im folgenden sollen jedoch sowohl Inhibitoren als auch Retarder als Inhibitoren verstanden werden. Sowohl bei der Lagerung als auch bei der chemisch und/oder physikalischen Behandlung (zum Beispiel bei der Destillation) von vinylisch ungesättigten Verbindungen, die radikalisch polymerisierbar sind, ist der Einsatz von Inhibitoren bzw. Retardern von Bedeutung.It is therefore common practice to use vinylically unsaturated compounds that are free radical are polymerizable and mixtures containing such compounds, compounds add that act as inhibitors or retarders of radical polymerization. Free radical polymerization during inhibitors - until complete Implementation with free radicals - prevent, retarders slow down the radical Polymerization. Inhibitors and retarders are generally under the generic term Stabilizers summarized. In the following, however, both inhibitors and Retarders can be understood as inhibitors. Both in storage and in chemical and / or physical treatment (for example in the distillation) of vinylically unsaturated compounds that can be polymerized by free radicals are used of inhibitors or retarders of importance.

Die US-A 4,187,382 betrifft ein Verfahren zur Veresterung von organischen Diolen mit Acrylsäure. Es wird empfohlen, das Diol mit Triphenylphosphit vorzubehandeln, um so die Neigung des Reaktionsgemisches zur radikalischen Polymerisation zu verringern. Als weitere inhibierende Komponente wird ein phenolischer Polymerisationsinhibitor vorgeschlagen.US-A 4,187,382 relates to a process for the esterification of organic diols with Acrylic acid. It is recommended to pretreat the diol with triphenyl phosphite in order to The tendency of the reaction mixture to reduce radical polymerization. As another inhibiting component is a phenolic polymerization inhibitor suggested.

Die DE-A 29 13 218 offenbart ein Verfahren zur Herstellung von Acrylsäureestern bzw. Methacrylsäureestern, bei dem als Polymerisationsinhibitor organische Phosphite zusammen mit phenolischen Polymerisationsinhibitoren eingesetzt werden.DE-A 29 13 218 discloses a process for the preparation of acrylic acid esters or Methacrylic acid esters in which organic phosphites are used as a polymerization inhibitor can be used together with phenolic polymerization inhibitors.

Vorstehend genannte Inhibitorkompositionen enthalten Phosphorverbindungen, die Phosphor in der Oxidationszahl +3 aufweisen und außerdem phenolische Verbindungen. Eine Zielsetzung ist, die Wirkung solcher Systeme bei der Stabilisierung von vinylisch ungesättigten Verbindungen weiter zu verbessern. The inhibitor compositions mentioned above contain phosphorus compounds which Have phosphorus in the oxidation number +3 and also phenolic compounds. One goal is to have the effect of such systems in stabilizing vinyl to further improve unsaturated compounds.

Die Aufgabe der vorliegenden Erfindung besteht darin, eine stark wirkende Inhibitorkomposition hervorzubringen, die Phosphor in der Oxidationszahl +3 aufweisende chemische Verbindungen und/oder phenolische Verbindungen enthält. Diese Inhibitorkomposition soll effektiv sein, wobei sich möglichst die inhibierende Wirkung der in ihr enthaltenen Komponenten in synergistischer Weise verstärken soll.The object of the present invention is a strong-acting To produce inhibitor composition, the phosphorus in the oxidation number +3 contains chemical compounds and / or phenolic compounds. This Inhibitor composition should be effective, the inhibitory effect of the components contained in it should reinforce in a synergistic manner.

Gelöst wird diese Aufgabe durch die Bereitstellung einer Inhibitorkomposition enthaltend als Komponenten a) wenigstens ein Nitroxyl-Radikal(derivat), b) wenigstens ein Phenol(derivat) und c) wenigstens eine weitere chemische Verbindung, welche mindestens ein Phosphoratom enthält, das die Oxidationszahl +3 aufweist.This object is achieved by providing an inhibitor composition containing as components a) at least one nitroxyl radical (derivative), b) at least one Phenol (derivative) and c) at least one further chemical compound which at least contains a phosphorus atom which has an oxidation number of +3.

Unter der Oxidationszahl eines Atoms innerhalb einer kovalenten Verbindung soll eine Zahl mit positivem oder negativem Vorzeichen verstanden werden, die die Ladung angibt, welches das Atom haben würde, wenn man die bindenden Elektronenpaare der kovalenten Bindungen, an denen das Atom teilnimmt, dem jeweils elektronegativeren Bindungspartner zuteilt. Bei Elektronenpaaren aus kovalenten Bindungen zwischen zwei gleichen Atomen enthält jedes Atom ein Elektron. Die Elektronegativität ist dabei als Maß anzusehen, wie stark ein Atom in einem Molekül bindende Elektronenpaare, die an dem Atom gebunden sind, anzieht. Die vorliegend relevanten Elektronegativitäten sind diejenigen gemäß H.R. Christen, Grundlagen der allgemeinen und anorganischen Chemie, Verlag Sauerländer, Aarau, Diesterweg-Salle, Frankfurt am Main (1973). Für die wichtigsten Elemente des Periodensystems weisen diese Elektronegativitäten die nachfolgenden Werte auf:
Be (1,5) ; B (2,0) ; H (2,1) ; C (2,5) ; Si (1,8) ; Ge (1,7) ; N (3,0) P (2,1) ; As (2,0) ; Sb (1,8) ; O (3,5) ; S (2,5) ; Se (2,4) ; Te (2,1) ; F (4,0) ; Cl (3,0) ; Br (2,8) ; J (2,4).The oxidation number of an atom within a covalent compound is to be understood as a number with a positive or negative sign, which indicates the charge that the atom would have if the binding electron pairs of the covalent bonds in which the atom takes part is the more electronegative binding partner allocated. With electron pairs from covalent bonds between two identical atoms, each atom contains one electron. Electronegativity is to be seen as a measure of how strongly an atom in a molecule attracts electron pairs that are bound to the atom. The relevant electronegativities are those according to HR Christen, Fundamentals of General and Inorganic Chemistry, Verlag Sauerländer, Aarau, Diesterweg-Salle, Frankfurt am Main (1973). These electronegativities have the following values for the most important elements of the periodic table:
Be (1.5); B (2.0); H (2.1); C (2.5); Si (1.8); Ge (1.7); N (3.0) P (2.1); As (2.0); Sb (1.8); O (3.5); S (2.5); Se (2.4); Te (2.1); F (4.0); Cl (3.0); Br (2.8); J (2.4).

Als Verbindungen (Komponente c)), welche mindestens ein die Oxidationszahl +3 aufweisendes Phosphoratom enthalten, können insbesondere Orthophos-phorige Säure oder ein Ester der Orthophosphorigen Säure eingesetzt werden. Ester der Orthophosphorigen Säure werden auch als Phosphite bezeichnet. Die Orthophosphorige Säure kann auch als Salz (meist als Alkalimetall- oder Ammoniumsalz) vorliegen. Bevorzugte Bindungspartner des Phosphors sind die Elemente C, S, O, N und/oder H.As compounds (component c)) which have at least one the oxidation number +3 containing phosphorus atom, in particular orthophosphorous acid or an ester of orthophosphorous acid can be used. Esters of Orthophosphorous acid are also known as phosphites. The orthophosphorous Acid can also be present as a salt (usually as an alkali metal or ammonium salt). Preferred binding partners of the phosphorus are the elements C, S, O, N and / or H.

Ferner kommen - insbesondere die als Stabilisatoren bekannten - Phosphonite (Ester der Phosphonigsäure) in Betracht.Furthermore come - in particular the known as stabilizers - phosphonites (esters of Phosphonous acid).

Zu besonders geeigneten Phosphiten (also der Ester der Orthophosphorigen Säure) und Phosphoniten (Ester der Phosphonigsäure) zählen beispielsweise Triphenylphosphit, Diphenylalkylphosphit, Phenyldialkylphosphit, Tris(nonylphenyl)phosphit, Trilaurylphosphit, Trioctadecylphosphit, Distearylphentaerythritoldiphosphit, Tris(2,4-di-tert.-butylphenyl)phosphit, Diisodecypentaerythritoldiphosphit, Bis(2,4-di-tert.-butylphenyl)pentaerythritol-diphosphit, Bis(2,6-di-tert-butyl-4-methylphenyl)pentaerythritoldiphosphit, Diisodecyloxypentaerythritoldiphosphit, Bis(2,4-di-tert.-butyl-6-methylphenyl)pentaerythritoldiphosphit, Bis(2,4,6-tris-(tert-butylphenyl))pentaerythritoldiphosphit, Tristearylsorbitoltriphosphit, Tetrakis(2,4-di-tert.-butylphenyl)-4,4'-biphenylendiphosphit, Tetrakis(2,4-di-tert.-butylphenyl)-4,4'-biphenylendiphosphonit, 6-Isooctyloxy-2,4,8,10-tetra-tert.-butyl-12H-dibenz-[d,g]-1,3,2-dioxaphosphocin, 6-Fluoro-2,4,8,10-tetra-tert.-butyl12-methyl-dibenz[d,g]-1,3,2-dioxaphosphocin, Bis(2,4-di-tert.-butyl-6-methylphenyl)methylphosphit und Bis(2,4-di-tert.-butyl-6-methylphenyl)ethylphosphit.
Mit Vorteil werden dabei Ester der Orthophosphorigen Säure (Phosphite) der allgemeinen Formel (I) oder Ester der Phosphonigsäure (Phosphonite) der allgemeinen Formel (II)

Figure 00040001
eingesetzt, wobei R, R', R'' gleich oder verschieden sein können und organische Reste insbesondere C1-C20-Alkyl, Hydroxy-C2-C4-alkyl, Halogen-C2-C4-alkyl, insbesondere Chloralkyl, -C6-C10-Aryl, insbesondere Phenyl oder durch C1-C8-Alkyl substituiertes Aryl (insbesondere durch C1-C4-Alkyl-substituiertes Phenyl) bedeuten. Auch können zwei der drei organischen Reste R, R' und R'' gemeinsam mit dem Phosphor und den beiden Sauerstoffatomen einen Heterocyclus (zum Beispiel 5- oder 6-atomig) bilden.Particularly suitable phosphites (that is, the esters of orthophosphorous acid) and phosphonites (esters of phosphonous acid) include, for example, triphenyl phosphite, diphenylalkyl phosphite, phenyl dialkyl phosphite, tris (nonylphenyl) phosphite, trilauryl phosphite, trioctadecyl phosphite, distearylphentaerythritol (2,4) butylphenyl) phosphite, diisodecypentaerythritol diphosphite, bis (2,4-di-tert-butylphenyl) pentaerythritol diphosphite, bis (2,6-di-tert-butyl-4-methylphenyl) pentaerythritol diphosphite, diisodecyloxypentaerythritol diphosphite, bis (2,4 -tert.-butyl-6-methylphenyl) pentaerythritol diphosphite, bis (2,4,6-tris (tert-butylphenyl)) pentaerythritol diphosphite, tristearyl sorbitol triphosphite, tetrakis (2,4-di-tert.-butylphenyl) -4.4 ' -biphenylene diphosphite, tetrakis (2,4-di-tert-butylphenyl) -4,4'-biphenylene diphosphonite, 6-isooctyloxy-2,4,8,10-tetra-tert-butyl-12H-dibenz- [d, g] -1,3,2-dioxaphosphocin, 6-fluoro-2,4,8,10-tetra-tert-butyl12-methyl-dibenz [d, g] -1,3,2-dioxaphosphocin, Bis (2,4-di-tert-butyl-6-methylphenyl) methyl phosphite and bis (2,4-di-tert-butyl-6-methylphenyl) ethyl phosphite.
It is advantageous to use esters of orthophosphorous acid (phosphites) of the general formula (I) or esters of phosphonous acid (phosphonites) of the general formula (II)
Figure 00040001
used, where R, R ', R''may be the same or different and organic radicals in particular C 1 -C 20 alkyl, hydroxy-C 2 -C 4 alkyl, halogen-C 2 -C 4 alkyl, especially chloroalkyl , -C 6 -C 10 aryl, especially phenyl or aryl substituted by C 1 -C 8 alkyl (especially phenyl substituted by C 1 -C 4 alkyl). Two of the three organic radicals R, R ′ and R ″ together with the phosphorus and the two oxygen atoms can also form a heterocycle (for example 5- or 6-atom).

Namentlich genannt seien Trimethyl-, Triethyl-, Tributyl-, Trihexyl-, Trioctyl-, Triphenyl, Tri-p-kresyl-, Trixylyl-, Tritolyl- und Tri-β-chlorethylphosphit. Aber auch Dimethyl-, Diethyl-, Dibutyl-, Dioctyl-, Diphenyl-, Ditolyl- und Dixylylphosphite sind erfindungsgemäß geeignete Inhibitoren. Besonders geeignet sind die unter den Markennamen Irgafos® 168 (Hersteller Ciba AG), Irgafos® P-EPQ (Hersteller Ciba AG) oder Ultranox® 626 (Hersteller GE-Speciality Chemicals GmbH) bekannten Spezies:

Figure 00050001
Figure 00060001
Trimethyl, triethyl, tributyl, trihexyl, trioctyl, triphenyl, tri-p-cresyl, trixylyl, tritolyl and tri-β-chloroethylphosphite may be mentioned by name. However, dimethyl, diethyl, dibutyl, dioctyl, diphenyl, ditolyl and dixylyl phosphites are also suitable inhibitors according to the invention. The species known under the brand names Irgafos® 168 (manufacturer Ciba AG), Irgafos® P-EPQ (manufacturer Ciba AG) or Ultranox® 626 (manufacturer GE-Specialty Chemicals GmbH) are particularly suitable:
Figure 00050001
Figure 00060001

Außerdem eignen sich als chemische Verbindungen, welche mindestens ein Phosphoratom enthalten, das die Oxidationszahl +3 aufweist, die Derivate der Phosphonigsäure R*-P(OH)2, mit R*=Alkyl (vorzugsweise C1- bis C8-Alkyl) oder Aryl, besonders C6-C10-Aryl (vorzugsweise Phenyl) und die Derivate der Phosphinigsäure der allgemeinen Formel (III)

Figure 00060002
mit R** unabhängig von R* - mit R*, R** = Alkyl (vorzugsweise C1- bis C20-Alkyl) oder Aryl, besonders C6-C10-Aryl (vorzugsweise Phenyl).Also suitable as chemical compounds which contain at least one phosphorus atom which has the oxidation number +3 are the derivatives of phosphonous acid R * -P (OH) 2 , with R * = alkyl (preferably C 1 -C 8 -alkyl) or Aryl, especially C 6 -C 10 aryl (preferably phenyl) and the derivatives of phosphinous acid of the general formula (III)
Figure 00060002
with R ** independently of R * - with R *, R ** = alkyl (preferably C 1 -C 20 -alkyl) or aryl, especially C 6 -C 10 -aryl (preferably phenyl).

Auch Derivate der bisher beschriebenen sauerstoffhaltigen Phosphorver-bindungen, welche mindestens ein die Oxidationszahl +3 aufweisendes Phosphoratom enthalten, bei denen ein oder mehrere O-Atome durch S oder NR* (R* hat dabei die gleiche Bedeutung wie vorstehend aufgeführt) ersetzt sind, sind geeignet.Derivatives of the oxygen-containing phosphorus compounds described so far, which contain at least one phosphorus atom with the oxidation number +3, at where one or more O atoms by S or NR * (R * has the same meaning as listed above) are suitable.

Neben ein oder mehreren chemischen Verbindungen, welche mindestens ein die Oxidationszahl +3 aufweisendes Phosphoratom enthalten, ist in der erfindungsgemäßen Inhibitorkomposition u.a. als weitere Komponente (weitere Inhibitorkomponente) noch wenigstens ein Nitroxyl-Radikal(derivat) als Komponente a) enthalten.In addition to one or more chemical compounds, at least one of which Oxidation number +3 containing phosphorus atom is in the invention Inhibitor composition and others as a further component (further inhibitor component) contain at least one nitroxyl radical (derivative) as component a).

Bevorzugt wird 4-Hydroxy-1-oxyl-2,2,6,6-tetramethylpiperidin als Nitroxyl-Radikal(derivat) eingesetzt. 4-Hydroxy-1-oxyl-2,2,6,6-tetramethylpiperidine is preferred as the nitroxyl radical (derivative) used.

Als geeignete Nitroxyl-Radikal(derivate) (auch als N-Oxyl-Radikale bezeichnet) kommen erfindungsgemäß prinzipiell alle Verbindungen in Betracht, die wenigstens eine >N-O· - Gruppe aufweisen. Die Nitroxyl-Radikal(derivate) können auch in situ aus anderen Verbindungen erzeugt werden, z.B. durch H-Abstraktion aus Hydroxylaminen oder durch Addition von C-Radikalen an Nitrone. Sie können aber auch aus aromatischen Aminen, die sich vom Anilin oder Phenylendiamin ableiten, in situ erzeugt werden. Als erfindungsgemäß geeignete Nitroxyl-Radikal(derivate) kommen vor allem diejenigen in Betracht, die sich von einem sekundären Amin ableiten, welches keine Wasserstoffatome an den α-C-Atomen trägt (d.h., die N-Oxyl-Gruppen leiten sich von entsprechenden sekundären Aminogruppen ab).Suitable nitroxyl radicals (derivatives) (also known as N-oxyl radicals) come according to the invention in principle all compounds which have at least one> N-O · - Have group. The nitroxyl radical (derivatives) can also be generated in situ from others Connections are created, e.g. by H abstraction from hydroxylamines or by Addition of C radicals to nitrons. You can also choose from aromatic amines that derived from aniline or phenylenediamine, generated in situ. As Nitroxyl radicals (derivatives) which are suitable according to the invention come primarily from those Consider that are derived from a secondary amine that does not contain hydrogen atoms on the α-C atoms (i.e., the N-oxyl groups derive from corresponding secondary amino groups).

Solche geeigneten, sich von einem sekundären Amin ableitenden, stabilen Nitroxyl-Radikal(derivate) sind z.B. jene der allgemeinen Formel (IV)

Figure 00070001
mit

R1, R2, R5 und R6 =
dieselben oder verschiedene gerad- oder verzweigtkettige, gegebenenfalls substituierte Alkylgruppen und
R3 und R4 =
dieselben oder verschiedene gerad- oder verzweigtkettige, gegebenenfalls substituierte Alkylgruppen oder
R3CNCR4 =
eine, gegebenenfalls substituierte, zyklische Struktur.
Suitable stable nitroxyl radicals (derivatives) derived from a secondary amine are, for example, those of the general formula (IV)
Figure 00070001
With
R 1 , R 2 , R 5 and R 6 =
the same or different straight or branched chain, optionally substituted alkyl groups and
R 3 and R 4 =
the same or different straight or branched chain, optionally substituted alkyl groups or
R 3 CNCR 4 =
an optionally substituted cyclic structure.

Beispiele für geeignete Verbindungen sind jene stabilen Nitroxyl-Radikal-(derivate) der allgemeinen Formel (IV), bei welchen R1, R2, R5 und R6 für (gleiche oder verschiedene) C1- bis C4-Alkylgruppen wie Methyl-, Ethyl-, n-Propyl-, iso-Propyl-, n-Butyl-, iso-Butyl- oder tert.-Butyl-, lineares oder verzweigtes Pentyl-, Phenyl- oder substituierte Gruppen hiervon und R3 und R4 für (gleiche oder verschiedene) C1- bis C4-Alkylgruppen wie Methyl-, Ethyl-, n-Propyl-, iso-Propyl-, n-Butyl-, iso-Butyl- oder tert.-Butyl-, lineares oder verzweigtes Pentyl-, substituierte Gruppen hiervon oder gemeinsam mit CNC für die zyklische Struktur

Figure 00080001
mit n gleich einer ganzen Zahl von 1 bis 10 (häufig 1 bis 6), einschließlich substituierter derartiger zyklischer Strukturen, stehen. Als beispielhafte Vertreter seien 2,2,6,6-Tetramethyl-1-oxyl-piperidin, 2,2,5,5-Tetramethyl-1-oxyl-pyrrolidin und 4-Oxo-2,2,6,6-tetramethyl-1-oxyl-piperidin genannt.Examples of suitable compounds are those stable nitroxyl radical (derivatives) of the general formula (IV) in which R 1 , R 2 , R 5 and R 6 represent (same or different) C 1 to C 4 alkyl groups such as methyl -, ethyl, n-propyl, iso-propyl, n-butyl, iso-butyl or tert-butyl, linear or branched pentyl, phenyl or substituted groups thereof and R 3 and R 4 for (Same or different) C 1 - to C 4 -alkyl groups such as methyl, ethyl, n-propyl, iso-propyl, n-butyl, iso-butyl or tert-butyl, linear or branched pentyl -, substituted groups of these or together with CNC for the cyclic structure
Figure 00080001
where n is an integer from 1 to 10 (often 1 to 6), including substituted such cyclic structures. Exemplary representatives include 2,2,6,6-tetramethyl-1-oxyl-piperidine, 2,2,5,5-tetramethyl-1-oxyl-pyrrolidine and 4-oxo-2,2,6,6-tetramethyl- Called 1-oxyl-piperidine.

Die N-Oxyl-Radikal(derivate) der allgemeinen Form (IV) lassen sich aus den entsprechenden sekundären Aminen durch Oxidation, z.B. mit Wasserstoffper-oxid, herstellen. In der Regel sind sie als Reinsubstanz darstellbar.The N-oxyl radical (derivatives) of the general form (IV) can be derived from the corresponding secondary amines by oxidation, e.g. with hydrogen peroxide, produce. As a rule, they can be represented as pure substances.

Zu den erfindungsgemäß geeigneten Nitroxyl-Radikal(derivaten) zählen insbe-sondere Piperidin- oder Pyrrolidin-N-Oxyle und Di-N-Oxyle der nachstehenden allgemeinen Formeln (V) bis (XII):

Figure 00090001
mit

  • m = 2 bis 10.
  • -R7, -R8, -R9 = unabhängig voneinander
    Figure 00100001
  • M⊕ = ein Wasserstoff- oder ein Alkalimetallion,
  • q = eine ganze Zahl von 1 bis 10,
  • R1', R2', R5', R6'= unabhängig voneinander und unabhängig von R1, R2, R5, R6 dieselben Gruppen wie R1,
  • R10 = C1- bis C4-Alkyl, -CH=CH2, -C≡CH, -CN,
    Figure 00100002
    ―COO⊖M⊕,―COOCH3 oder ―COOC2H5,
  • R11 = ein organischer Rest, der wenigstens eine primäre, sekundäre (z.B.-NHR1) oder tertiäre Aminogruppe (z.B. -NR1R2) oder wenigstens eine Ammoniumgruppe - N⊕R14R15R16X⊖ aufweist, mit X⊖ = F⊖, Cl⊖, Br⊖, HSO4 ⊖, SO4 2⊖, H2PO4 ⊖, HPO4 2⊖ oder PO4 3⊖ und R14, R15, R16 voneinander unabhängige organische Reste (z.B. unabhängig voneinander und unabhängig von R1 dieselben Gruppen wie R1),
  • R12 = unabhängig von R11 dieselben Gruppen wie R11 oder -H, -OH, C1- bis C4-Alkyl, - COO⊖M⊕, -C≡CH,
    Figure 00110001
    oder hydroxysubstituiertes C1- bis C4-Alkyl (z.B. hydroxyethyl oder hydroxypropyl) oder
  • R11, R12 =gemeinsam den Sauerstoff einer Carbonylgruppe und
  • R13 ―H,―CH3 oder
    Figure 00110002
    • The nitroxyl radicals (derivatives) suitable according to the invention include in particular piperidine or pyrrolidine N-oxyls and di-N-oxyls of the following general formulas (V) to (XII):
    Figure 00090001
    With
  • m = 2 to 10.
  • -R 7 , -R 8 , -R 9 = independently of each other
    Figure 00100001
  • M ⊕ = a hydrogen or an alkali metal ion,
  • q = an integer from 1 to 10,
  • R 1 ' , R 2' , R 5 ' , R 6' = independently of one another and independently of R 1 , R 2 , R 5 , R 6 the same groups as R 1 ,
  • R 10 = C 1 to C 4 alkyl, -CH = CH 2 , -C ,CH, -CN,
    Figure 00100002
    ―COO ⊖ M ⊕ , ―COOCH 3 or ―COOC 2 H 5 ,
  • R 11 = an organic radical which has at least one primary, secondary (eg -NHR 1 ) or tertiary amino group (eg -NR 1 R 2 ) or at least one ammonium group - N ⊕ R 14 R 15 R 16 X ⊖ , with X ⊖ = F ⊖ , Cl ⊖ , Br ⊖ , HSO 4 ⊖ , SO 4 2⊖ , H 2 PO 4 ⊖ , HPO 4 2⊖ or PO 4 3⊖ and R 14 , R 15 , R 16 independent organic radicals (e.g. independently from each other and independently of R 1, the same groups as R 1 ),
  • R 12 = independently of R 11 the same groups as R 11 or -H, -OH, C 1 - to C 4 -alkyl, - COO ⊖ M ⊕ , -C≡CH,
    Figure 00110001
    or hydroxy-substituted C 1 to C 4 alkyl (for example hydroxyethyl or hydroxypropyl) or
  • R 11 , R 12 = together the oxygen of a carbonyl group and
  • R 13 ―H, ―CH 3 or
    Figure 00110002
    •

    Vorzugsweise ist R1 = R2 = R5 = R6 = R1' = R2' = R5' = R6' = -CH3.Preferably R 1 = R 2 = R 5 = R 6 = R 1 ' = R 2' = R 5 ' = R 6' = -CH 3 .

    Als beispielhafte Vertreter erfindungsgemäß geeigneter N-Oxyl-Radikal(derivate) seien 1-Oxyl-2,2,6,6-tetramethylpiperidin, 1-Oxyl-2,2,6,6-tetramethylpiperidin-4-ol, 1-Oxyl-2,2,6,6-tetramethyl-4-methoxypiperidin, 1-Oxyl-2,2,6,6-tetramethyl-4-ethoxypiperidin, 1-Oxyl-2,2,6,6-tetramethyl-4-trimethylsiloxypiperidin, 1-Oxyl-2,2,6,6-tetramethylpiperidin-4-on, 1-Oxyl-2,2,6,6-tetramethylpiperidin-4-yl-acetat, 1-Oxyl-2,2,6,6-tetramethylpiperidin-4-yl-2-ethylhexanoat, 1-Oxyl-2,2,6,6-tetramethylpiperidin-4-yl-stearat, 1-Oxyl-2,2,6,6-tetramethylpiperidin-4-yl-benzoat, 1-Oxyl-2,2,6,6-tetramethylpiperidin-4-yl-(4-tert-butyl)benzoat, Bis(1-oxyl-2,2,6,6-tetramethylpiperidin-4-yl)-succinat, Bis(1-oxyl-2,2,6,6-tetramethyl-piperidin-4-yl)-adipat, Bis(1-oxyl-2,2,6,6-tetramethylpiperidin-4-yl)-sebacat, Bis(1-oxyl-2,2,6,6-tetramethylpiperidin-4-yl)-n-butylmalonat, Bis(1-oxyl-2,2,-6,6-tetramethylpiperidin-4-yl)-phthalat, Bis(1-oxyl-2,2,6,6-tetramethylpiperidin-4-yl)-isophthalat, Bis(1-oxyl-2,2,6,6-tetramethylpiperidin-4-yl)-terephthalat, Bis(1-oxyl-2,2,6,6-tetramethylpiperidin-4-yl)-hexahydroterephthalat, N,N'-Bis-(1-oxyl-2,2,6,6-tetramethylpiperidin-4-yl)-adipinamid, N-(1-Oxyl-2,2,6,6-tetra-methylpiperidin-4-yl)-caprolactam, N-(1-Oxyl-2,2,6,6-tetra-methylpiperidin-4-yl)-dodecylsuccinimid, 2,4,6-Tris-[N-butyl-N-(1-oxyl-2,2,6,6-tetramethyl-piperidin-4-yl]-s-triazin, N,N'-Bis(1-oxyl-2,2,6,6-tetramethylpiperidin-4-yl)-N,N'-bis-formyl-1,6-diaminohexan, 4,4'-Ethylen-bis(1-oxyl-2,2,6,6-tetramethyl-piperazin-3-on) und Tris-(2,2,6,6-tetramethyl-1-oxyl-piperidin-4-yl)phosphit sowie zusätzlich noch 1-Oxyl-2,2,6,6-tetramethyl-1,2,3,6-tetrahydropyridin genannt.Exemplary representatives of N-oxyl radicals (derivatives) suitable according to the invention are 1-oxyl-2,2,6,6-tetramethylpiperidine, 1-oxyl-2,2,6,6-tetramethylpiperidin-4-ol, 1-oxyl-2,2,6,6-tetramethyl-4-methoxypiperidine, 1-oxyl-2,2,6,6-tetramethyl-4-ethoxypiperidine, 1-oxyl-2,2,6,6-tetramethyl-4-trimethylsiloxypiperidine, 1-oxyl-2,2,6,6-tetramethylpiperidin-4-one, 1-oxyl-2,2,6,6-tetramethylpiperidin-4-yl acetate, 1-oxyl-2,2,6,6-tetramethylpiperidin-4-yl-2-ethylhexanoate, 1-oxyl-2,2,6,6-tetramethylpiperidin-4-yl stearate, 1-oxyl-2,2,6,6-tetramethylpiperidin-4-yl benzoate, 1-oxyl-2,2,6,6-tetramethylpiperidin-4-yl- (4-tert-butyl) benzoate, Bis (1-oxyl-2,2,6,6-tetramethylpiperidin-4-yl) succinate, bis (1-oxyl-2,2,6,6-tetramethylpiperidin-4-yl) adipate, Bis (1-oxyl-2,2,6,6-tetramethylpiperidin-4-yl) sebacate, Bis (1-oxyl-2,2,6,6-tetramethylpiperidin-4-yl) -n-butylmalonate, bis (1-oxyl-2,2, -6,6-tetramethylpiperidin-4-yl) phthalate, Bis (1-oxyl-2,2,6,6-tetramethylpiperidin-4-yl) isophthalate, Bis (1-oxyl-2,2,6,6-tetramethylpiperidin-4-yl) terephthalate, bis (1-oxyl-2,2,6,6-tetramethylpiperidin-4-yl) hexahydroterephthalate, N, N'-bis (1-oxyl-2,2,6,6-tetramethylpiperidin-4-yl) adipinamide, N- (1-oxyl-2,2,6,6-tetra-methylpiperidin-4-yl) caprolactam, N- (1-oxyl-2,2,6,6-tetra-methylpiperidin-4-yl) dodecylsuccinimide, 2,4,6-tris [N-butyl-N- (1-oxyl-2,2, 6,6-tetramethyl-piperidin-4-yl] -s-triazine, N, N'-bis (1-oxyl-2,2,6,6-tetramethylpiperidin-4-yl) -N, N'-bis-formyl-1,6-diaminohexane, 4,4'-ethylene-bis (1-oxyl-2,2,6,6-tetramethyl-piperazin-3-one) and tris (2,2,6,6-tetramethyl-1-oxyl-piperidin-4-yl) phosphite and additionally 1-oxyl-2,2,6,6-tetramethyl-1,2,3,6-tetrahydropyridine called.

    Weitere geeignete beispielhafte Vertreter (bei den entsprechenden Strukturformeln sind H-Atome nicht eingezeichnet) sind:

    Figure 00120001
    Figure 00130001
    Figure 00140001
    Figure 00150001
    Figure 00160001
    Figure 00170001
    Figure 00180001
    Other suitable representative examples (H atoms are not shown in the corresponding structural formulas) are:
    Figure 00120001
    Figure 00130001
    Figure 00140001
    Figure 00150001
    Figure 00160001
    Figure 00170001
    Figure 00180001

    Selbstverständlich können erfindungsgemäß auch Gemische von N-Oxyl-Radikal(derivaten) eingesetzt werden. Of course, mixtures of N-oxyl radical (derivatives) be used.

    Die Inhibitorkomposition enthält als weitere Komponente - Komponente b) - noch wenigstens ein Phenol(derivat) (als Phenolderivat kommt auch Phenol als solches in Frage). Als Phenolderivat wird bevorzugt ein Phenol oder Kresol, bei dem ein oder mehrere Wasserstoffatome durch Tert.-Butyl-Gruppen substituiert sind, insbesondere 2,6-Di-tert.-butylkresol, oder Hydrochinone, insbesondere Hydrochinonmonomethylether, eingesetzt. Außerdem kommen Phenole oder Kresole in Frage, bei denen ein oder mehrere Wasserstoffatome durch i-Propyl-Gruppen substituiert sind, wie Thymol oder Carvacrol. Außerdem eignen sich Brenzkatechin und dessen Derivate sowie Resorcin und dessen Derivate. Wie vorstehend beschrieben, eignen sich als zweiwertige Phenole auch Hydrochinon und dessen Derivate, insbesondere Ether des Hydrochinons wie Hydrochinonmonomethylether. Naphthole, wie α-Naphthol und Vitamin E kommen ebenfalls in Frage. Außerdem eignen sich auch Phenole, die über Alkylbrücken miteinander verbunden sind, wie Bisphenol A. Allgemein eignen sich als Phenolderivate Verbindungen, die ein Oxylradikal bilden können, das an ein aromatisches System gebunden ist. Dies geschieht durch homolytische Spaltung einer Sauerstoff-Wasserstoffbindung, wobei das Sauerstoffatom an ein aromatisches System gebunden ist. Besonders bevorzugte Phenolderivate werden durch die folgende allgemeine Strukturformel (XIII) wiedergegeben:

    Figure 00190001
    The inhibitor composition contains, as a further component - component b) - at least one phenol (derivative) (phenol as such is also suitable as a phenol derivative). A phenol or cresol in which one or more hydrogen atoms are substituted by tert-butyl groups, in particular 2,6-di-tert-butylcresol, or hydroquinones, in particular hydroquinone monomethyl ether, is preferably used as the phenol derivative. Also suitable are phenols or cresols in which one or more hydrogen atoms are substituted by i-propyl groups, such as thymol or carvacrol. Pyrocatechol and its derivatives as well as resorcinol and its derivatives are also suitable. As described above, hydroquinone and its derivatives, in particular hydroquinone ethers such as hydroquinone monomethyl ether, are also suitable as dihydric phenols. Naphthols such as α-naphthol and vitamin E are also suitable. Also suitable are phenols which are connected to one another via alkyl bridges, such as bisphenol A. In general, suitable phenol derivatives are compounds which can form an oxyl radical which is bonded to an aromatic system. This is done by homolytic cleavage of an oxygen-hydrogen bond, the oxygen atom being bound to an aromatic system. Particularly preferred phenol derivatives are represented by the following general structural formula (XIII):
    Figure 00190001

    Dabei sind R1, R2, R3, R4, und R5 gleich oder verschieden und bedeuten H, Halogen, C1 bis C20 - Alkyl oder Aryl, SO3H, SO3 -M+, OH, SH, O-Alkyl, O-Aryl, S-Alkyl, S-Aryl, NH-Akyl, NH-Aryl, NO, NO2, NH-OH, NH2, COOH, CN, O-CO-R6, O-CO-O-R6, NH-CO-R6, CN(-OH)-(R6), CO-O-R6 oder CO-NH-R6, wobei R6 = H, Halogen, C1 bis C20 - Alkyl oder Aryl, SO3H, SO3 -M+, OH, SH, O-Alkyl, O-Aryl, S-Alkyl, S-Aryl, NH-Akyl, NH-Aryl, NO, NO2, NH-OH, NH2, COOH oder CN. Here, R 1, R 2, R 3, R 4, and R 5 are identical or different and denote H, halogen, C 1 to C 20 - alkyl or aryl, SO 3 H, SO 3 - M +, OH, SH, O-alkyl, O-aryl, S-alkyl, S-aryl, NH-Akyl, NH-aryl, NO, NO 2 , NH-OH, NH 2 , COOH, CN, O-CO-R6, O-CO- OR 6 , NH-CO-R 6 , CN (-OH) - (R 6 ), CO-OR 6 or CO-NH-R 6 , where R 6 = H, halogen, C 1 to C 20 - alkyl or aryl , SO 3 H, SO 3 - M + , OH, SH, O-alkyl, O-aryl, S-alkyl, S-aryl, NH-Akyl, NH-aryl, NO, NO 2 , NH-OH, NH 2 , COOH or CN.

    Die Inhibitorkomposition enthaltend ein oder mehrere chemische Verbindungen, welche mindestens ein die Oxidationszahl +3 aufweisendes Phosphoratom enthalten, sowie ein oder mehrere Nitroxyl-Radikal(derivate) und ein oder mehrere Phenol(derivate), weist eine besonders gute stabilisierende Wirkung auf Bezüglich der Wirkung als Inhibitor bei der radikalischen Polymerisation weist die erfindungsgemäße Inhibitorkomposition synergistische Eigenschaften auf - Spezies der drei verschiedenen Inhibitorkomponenten verstärken sich gegenseitig in ihrer inhibierenden Wirkung. Demgemäß ist die inhibierende Wirkung der erfindungsgemäßen Kombination besser als die inhibierende Wirkung, die zum Beispiel beim alleinigen Vorliegen der einzelnen Komponenten vorhanden wäre, oder als die Addition der Einzelwirkungen.The inhibitor composition containing one or more chemical compounds which contain at least one phosphorus atom with the oxidation number +3, and one or more nitroxyl radical (derivatives) and one or more phenol (derivatives) has one particularly good stabilizing effect on the effect as an inhibitor in the The inhibitor composition according to the invention exhibits radical polymerization synergistic properties on - species of the three different inhibitor components reinforce each other in their inhibitory effect. Accordingly, the inhibitory Effect of the combination of the invention better than the inhibitory effect that for example if only the individual components were present, or than the addition of the individual effects.

    Günstig ist, daß die erfindungsgemäße Inhibitorkomposition ihre Wirksamkeit auch im Beisein von molekularem Sauerstoff entfaltet.It is favorable that the inhibitor composition according to the invention is also effective in Developed in the presence of molecular oxygen.

    Im folgenden soll auf besonders geeignete Inhibitorkompositionen eingegangen werden. Dabei sind Komponenten, die in diesen Inhibitorkompositionen enthalten sind, in der nachstehenden Tabelle aufgeführt - die Kombination folgender Komponenten erweist sich als besonders günstig:

    Figure 00200001
    Figure 00210001
    Figure 00220001
    Figure 00230001
    Figure 00240001
    Figure 00250001
    Figure 00260001
    Figure 00270001
    Figure 00280001
    Figure 00290001
    Figure 00300001
    Figure 00310001
    Figure 00320001
    Figure 00330001
    Figure 00340001
    Figure 00350001
    In the following, particularly suitable inhibitor compositions will be discussed. Components contained in these inhibitor compositions are listed in the table below - the combination of the following components has proven to be particularly advantageous:
    Figure 00200001
    Figure 00210001
    Figure 00220001
    Figure 00230001
    Figure 00240001
    Figure 00250001
    Figure 00260001
    Figure 00270001
    Figure 00280001
    Figure 00290001
    Figure 00300001
    Figure 00310001
    Figure 00320001
    Figure 00330001
    Figure 00340001
    Figure 00350001

    Der besondere Vorteil der erfindungsgemäßen Inhibitorkomposition - der

    Figure 00350002
    Dreierkombination" - ist, daß insgesamt nur wenig Inhibitor benötigt wird.The particular advantage of the inhibitor composition according to the invention - the
    Figure 00350002
    Combination of three "- is that overall little inhibitor is needed.

    Bei Rektifikations- und Destillationsverfahren wird vergleichsweise weniger Polymer abgeschieden, falls das erfindungsgemäße Inhibitorsystem eingesetzt wird, so daß die entsprechenden Anlagen weniger oft wegen Reinigungsarbeiten abgestellt werden müssen. Außerdem sorgt das synergistisch wirkende Inhibitorsystem dafür, daß weniger Monomer durch Polymerisation verbraucht wird und somit verloren geht".In the case of rectification and distillation processes, comparatively less polymer is deposited if the inhibitor system according to the invention is used, so that the corresponding plants have to be shut down less often because of cleaning work. In addition, the synergistic inhibitor system ensures that less monomer is consumed by polymerization and thus get lost".

    Selbstverständlich kann die Inhibitorkomposition neben den beschriebenen Inhibitoren - Phosphorverbindungen, Nitroxyl-Radikal(derivate), Phenol(derivate) - noch weitere eine radikalische Polymerisation inhibierende Bestandteile enthalten. Beispiele für solche sonstigen radikalischen Polymerisationsinhibitoren sind organische Nitrosoverbindungen wie N-Nitrosoarylamine. Diese Inhibitorkompositionen haben auch Wirksamkeit bei Anwesenheit von molekularem Sauerstoff.Of course, the inhibitor composition in addition to the described inhibitors - Phosphorus compounds, nitroxyl radical (derivatives), phenol (derivatives) - yet another one contain radical polymerization inhibiting components. Examples of such Other radical polymerization inhibitors are organic nitroso compounds such as N-nitrosoarylamines. These inhibitor compositions also have efficacy Presence of molecular oxygen.

    Die Inhibitorkompositionen werden erfindungsgemäß zur Stabilisierung von Reinsubstanzen, die mindestens eine vinylisch ungesättigte Gruppe aufweisen oder von Gemischen, die wenigstens eine Substanz enthalten, welche mindestens eine vinylisch ungesättigte Gruppe aufweist, verwendet. Die Inhibitorkomposition wirkt auch in Anwesenheit von Sauerstoff.According to the invention, the inhibitor compositions are used to stabilize Pure substances which have at least one vinylically unsaturated group or of Mixtures that contain at least one substance that contains at least one vinyl has unsaturated group used. The inhibitor composition also works in Presence of oxygen.

    Erfindungsgemäß wird auch ein Gemisch bereitgestellt, enthaltend wenigstens eine Verbindung, die mindestens eine vinylisch ungesättigte Gruppe aufweist und eine erfindungsgemäße Inhibitorkomposition.According to the invention, a mixture comprising at least one is also provided Compound which has at least one vinylically unsaturated group and one inhibitor composition according to the invention.

    Das Gemisch enthält in der Regel ein oder mehrere chemische Verbindungen, welche mindestens ein die Oxidationszahl +3 aufweisendes Phosphoratom enthalten, in einer Gesamtkonzentration von 1 bis 5000 ppm, bevorzugt von 5 bis 1000 ppm, sowie ein oder mehrere Nitroxyl-Radikal(derivate) in einer Gesamtkonzentration von 1 bis 3000 ppm, bevorzugt von 5 bis 300 ppm und ein oder mehrere Phenolderivate in einer Gesamtkonzentration von 1 bis 3000 ppm, bevorzugt von 5 bis 1500 ppm.The mixture usually contains one or more chemical compounds, which contain at least one phosphorus atom having the oxidation number +3, in one Total concentration from 1 to 5000 ppm, preferably from 5 to 1000 ppm, and one or several nitroxyl radicals (derivatives) in a total concentration of 1 to 3000 ppm, preferably from 5 to 300 ppm and one or more phenol derivatives in one Total concentration from 1 to 3000 ppm, preferably from 5 to 1500 ppm.

    Unter den Verbindungen, die mindestens eine vinylisch ungesättigte Gruppe aufweisen, sind insbesondere solche zu verstehen, die sich radikalisch homo- und/oder copolymerisieren lassen. Das sind zum Beispiel Olefine, wie Isobuten, Ethylen oder Propylen, vinylaromatische Monomere wie Styrol, α-Methylstyrol, o-Chlorstyrol oder Vinyltoluole, C4-C8-konjugierte Diene wie Butadien oder Isopren, Ester aus Vinylalkohol und 1 bis 18 C-Atome aufweisenden Monocarbonsäuren wie Vinylacetat, Vinylpropionat, Vinyl-n-butyrat, Vinyllaurat oder Vinylstearat. Insbesondere sind auch 3 bis 6 C-Atome aufweisende α, β-monoethylenisch ungesättigte Mono- und Dicarbonsäuren, wie insbesondere Acrylsäure, Methacrylsäure, Maleinsäure, Fumarsäure und Itaconsäure, die Ester aus den vorgenannten Carbonsäuren und 1 bis 12, bevorzugt 1 bis 4 C-Atome aufweisenden Alkanolen, wie insbesondere Acrylsäure- und Methacrylsäure-methyl-ethyl-, -n-butyl-, -iso-butyl-, -tert.-butyl- und -2-ethylhexyl-ester; Maleinsäuredimethylester oder Maleinsäuredi-n-butylester, geeignet.The compounds which have at least one vinylically unsaturated group are to be understood in particular to be those which can be homopolymerized and / or copolymerized by free radicals. Examples include olefins such as isobutene, ethylene or propylene, vinyl aromatic monomers such as styrene, α-methylstyrene, o-chlorostyrene or vinyltoluenes, C 4 -C 8 -conjugated dienes such as butadiene or isoprene, esters from vinyl alcohol and 1 to 18 C- Atomic monocarboxylic acids such as vinyl acetate, vinyl propionate, vinyl n-butyrate, vinyl laurate or vinyl stearate. In particular, 3 to 6 carbon atoms are α, β-monoethylenically unsaturated mono- and dicarboxylic acids, such as in particular acrylic acid, methacrylic acid, maleic acid, fumaric acid and itaconic acid, the esters of the aforementioned carboxylic acids and 1 to 12, preferably 1 to 4, C- Alkanols containing atoms, such as, in particular, methyl, ethyl, n-butyl, isobutyl, tert-butyl and 2-ethylhexyl acrylate and methacrylic acid; Maleic acid dimethyl ester or maleic acid di-n-butyl ester, is suitable.

    Es eignen sich jedoch auch Vorläuferaldehyde, Nitrile und Amide der vorgenannten 3 bis 6 C-Atome aufweisenden α,β-monoethylenisch ungesättigten Mono- und Dicarbonsäuren, zum Beispiel Acrolein, Methacrolein, Acrylnitril, Methacrylnitril, Acrylamid und Methacrylamid. Monomere wie Vinylsulfonsäure, Vinylphosphonsäure, N-Vinylimidazol und N-Vinylpyrrolidon kommen auch in Frage.However, precursor aldehydes, nitriles and amides of the aforementioned 3 to 6 are also suitable Α, β-monoethylenically unsaturated mono- and dicarboxylic acids containing C atoms, for example acrolein, methacrolein, acrylonitrile, methacrylonitrile, acrylamide and Methacrylamide. Monomers such as vinyl sulfonic acid, vinyl phosphonic acid, N-vinylimidazole and N-vinyl pyrrolidone are also suitable.

    Die erfindungsgemäße Inhibitorkomposition ist als Zusatz sowohl zur Lagerstabilisierung als auch für die Prozeßstabilisierung (Herstellung, Reinigung und chemische Umsetzung) von wenigstens eine vinylisch ungesättigte Gruppe aufweisenden Verbindungen geeignet. Letzteres gilt insbesondere auch für destillative Prozesse, die in der Regel bei Temperaturen von 50 bis 300 °C, bevorzugt bei 50 bis 200 °C, besonders bevorzugt bei 50 bis 150 °C, ablaufen.The inhibitor composition according to the invention is an additive both for storage stabilization as well as for process stabilization (manufacturing, cleaning and chemical conversion) of compounds containing at least one vinylically unsaturated group. The latter also applies in particular to distillative processes that are usually involved Temperatures from 50 to 300 ° C, preferably at 50 to 200 ° C, particularly preferably at 50 up to 150 ° C.

    Insbesondere eignet sich die Stabilisierung mit der erfindungsgemäßen Inhibitorkomposition bei der destillativen (rektifikativen) Behandlung von (Meth)acrylsäureestern (insbesondere der vorgenannten beispielhaften Vertreter), bei deren destillativer oder rektifikativer Abtrennung aus Produktgemischen, wie sie als Ergebnis einer säurekatalysierten Veresterung von (Meth)acrylsäure mit Alkoholen, insbesondere Alkanolen (insbesondere C1- bis C12- bzw. C1- bis C8-Alkanolen) vor und/oder nach Abtrennung des Säurekatalysators vorliegen.The stabilization with the inhibitor composition according to the invention is particularly suitable for the distillative (rectificative) treatment of (meth) acrylic acid esters (in particular the aforementioned exemplary representatives), for their distillative or rectificative separation from product mixtures, such as is the result of an acid-catalyzed esterification of (meth) acrylic acid with alcohols, in particular alkanols (in particular C 1 to C 12 or C 1 to C 8 alkanols) before and / or after removal of the acid catalyst.

    Diese eignet sich aber auch zur Stabilisierung von vorgenannten (Meth)-acrylsäureester enthaltenden Gemischen, die weder Veresterungskatalysator noch Acryl- oder Methacrylsäure selbst enthalten. Solche (Meth)acrylsäureester enthaltende Gemische bilden beispielsweise vorgenannte Veresterungsprodukt-gemische nach zum Beispiel extraktiver und/oder rektifikativer Abtrennung des Säurekatalysators sowie nach entsprechender Abtrennung der überschüssigen (Meth)acrylsäure.However, this is also suitable for stabilizing the aforementioned (meth) acrylic acid esters containing mixtures that are neither esterification catalyst nor acrylic or Methacrylic acid itself included. Such mixtures containing (meth) acrylic esters form, for example, the aforementioned esterification product mixtures, for example extractive and / or rectificative separation of the acid catalyst and after appropriate removal of the excess (meth) acrylic acid.

    Die Stabilisierung eines einer Destillation oder Rektifikation unterworfenen (Meth)acrylsäureester enthaltenden Gemisches kann so erfolgen, daß man die Inhibitoren dem Gemisch bereits vor der Destillation zusetzt.The stabilization of one subjected to distillation or rectification Mixture containing (meth) acrylic acid esters can be such that the inhibitors already added to the mixture before distillation.

    Zusätzlich kann zur Stabilisierung eine Inhibitorzugabe auf den Kopf der Kolonne erfolgen. Selbstverständlich kann auch die gesamte Stabilisierung ausschließlich durch eine Inhibitorzugabe auf den Kolonnenkopf erfolgen. In addition, an inhibitor can be added to the top of the column for stabilization respectively. Of course, the entire stabilization can only be done by inhibitor is added to the top of the column.

    Die verschiedenen Komponenten der erfindungsgemäßen Inhibitorkomposition können zeitlich nacheinander, simultan oder auch bereits vorgemischt zugesetzt werden. Das vorgenannte gilt auch für die anderen Inhibitoren, falls das Inhibitorkomposition solche umfaßt.The various components of the inhibitor composition according to the invention can added sequentially, simultaneously or even premixed. The the aforementioned also applies to the other inhibitors, if the inhibitor composition is one includes.

    Auch kann die Zugabe der Komponenten der Inhibitorkomposition an unterschiedlichen Zugabeorten vorgenommen werden. So können zum Beispiel Komponenten des Inhibitorsystems am Kopf der Rektifikationskolonne und andere Komponenten des Inhibitorsystems in den Sumpf und/oder den Zulauf der Rektifikationskolonne gegeben werden. Dies gilt sowohl für solche Retifikationen im Rahmen derer der (Meth)acrylsäureester über Kopf-, über Sumpf- und/oder über Seitenabzug abgetrennt wird. Auch kann es zweckmäßig sein, das erfindungsgemäße Verfahren im Fall einer kontinuierlichen destillativen (retifikativen) Abtrennung von (Meth)acrylsäureestern so durchzuführen, daß wenigstens eine zuzuführende Inhibitorkomponente nicht kontinuierlich, sondern lediglich von Zeit zu Zeit, d.h. periodisch wiederkehrend, zugegeben wird (z.B. am Kolonnenkopf, im Sumpf und/oder im Zulauf).The addition of the components of the inhibitor composition to different Addition locations are made. For example, components of the Inhibitor systems at the top of the rectification column and other components of the Inhibitor systems in the bottom and / or the inlet of the rectification column become. This applies both to such retifications as part of the (Meth) acrylic acid esters are removed via the top, bottom and / or side draw becomes. It can also be expedient to use the method according to the invention in the case of a continuous distillative (retificative) separation of (meth) acrylic esters perform that at least one inhibitor component to be supplied continuously, but only from time to time, i.e. recurring, is added (e.g. at the top of the column, in the bottom and / or in the feed).

    Alles über die Stabilisierung bei der destillativen (rektifikativen) Abtrennung von (Meth)acrylsäureestern aus säurekatalysierten Veresterungsgemischen beschriebene, gilt in gleicher Weise auch bezüglich einer destillativen (rektifikativen) Abtrennung von (Meth)acrylsäure bzw. (Meth)acrolein aus diese enthaltenden Gemischen.All about stabilization in the distillative (rectificative) separation of (Meth) acrylic acid esters described from acid-catalyzed esterification mixtures applies in same also with regard to a distillative (rectificative) separation of (Meth) acrylic acid or (meth) acrolein from mixtures containing these.

    Unter anderem ist (Meth)acrylsäure durch katalytische Gasphasenoxidation von Alkanen, Alkanolen, Alkenen oder Alkenalen erhältlich, die 3 bzw. 4 C-Atome enthalten. Besonders vorteilhaft ist (Meth)acrylsäure z.B. durch katalytische Gasphasenoxidation von Propan, Propen, tert.-Butanol, iso-Buten, iso-Butan, iso-Butyraldehyd oder Methacrolein erhältlich. Als Ausgangsverbindungen sind aber auch solche denkbar, aus welchen sich die eigentliche C3-/C4-Ausgangsver-bindung während der Gasphasenoxidation erst intermediär bildet. Beispielhaft genannt sei der Methylether des tert.-Butanols. Among other things, (meth) acrylic acid can be obtained by catalytic gas phase oxidation of alkanes, alkanols, alkenes or alkenals which contain 3 or 4 carbon atoms. (Meth) acrylic acid is particularly advantageously obtainable, for example, by catalytic gas phase oxidation of propane, propene, tert-butanol, isobutene, isobutane, isobutyraldehyde or methacrolein. However, starting compounds are also conceivable from which the actual C 3 - / C 4 starting compound only forms intermediately during the gas phase oxidation. The methyl ether of tert-butanol may be mentioned as an example.

    Dabei werden diese Ausgangsgase, in der Regel mit Inertgasen wie Stickstoff, CO, CO2, gesättigten Kohlenwasserstoffen und/oder Wasserdampf verdünnt, im Gemisch mit Sauerstoff bei erhöhten Temperaturen (üblicherweise 200 bis 400°C) sowie gegebenenfalls erhöhtem Druck über übergangsmetallische (z.B. Mo, V, W und/oder Fe enthaltende) Mischoxidkatalysatoren geleitet und oxidativ in die (Meth)acrylsäure umgewandelt.These starting gases are usually diluted with inert gases such as nitrogen, CO, CO 2 , saturated hydrocarbons and / or water vapor, in a mixture with oxygen at elevated temperatures (usually 200 to 400 ° C) as well as optionally increased pressure via transition metals (e.g. Mo , V, W and / or Fe) mixed oxide catalysts passed and oxidatively converted into (meth) acrylic acid.

    Aufgrund zahlreicher im Verlauf der katalytischen Gasphasenoxidation erfolgender Parallel- und Folgereaktionen sowie aufgrund der mitzuver-wendenden inerten Verdünnungsphase wird bei der katalytischen Gasphasenoxidation jedoch keine reine (Meth)acrylsäure, sondern ein Reaktionsgemisch erhalten, das im wesentlichen (Meth)acrylsäure, die inerten Verdünnungsgase und Nebenprodukte enthält, aus welchem die (Meth)acrylsäure abgetrennt werden muß. Neben von (Meth)acrylsäure vergleichsweise einfach zu entfernenden und bei Folgeverwendungen der (Meth)acrylsäure weniger störenden Nebenprodukten wie Essigsäure, enthält das Reaktionsgasgemisch häufig auch mit (Meth)acrylsäure eng verwandte und daher von (Meth)acrylsäure schwer abtrennbare niedere Aldehyde wie Formaldehyd, Acetaldehyd, Acrolein, Methacrolein, Propionaldehyd, n-Butyraldehyd, Benzaldehyd, Furfural und Crotonaldehyd sowie zusätzlich gegebenenfalls Maleinsäureanhydrid (bezogen auf die im Reaktionsgasgemisch enthaltende Menge an (Meth)acrylsäure beträgt die Gesamtmenge dieser, bei Folgeverwendungen häufig erheblich störenden, Nebenkomponenten in der Regel ≤ 2 Gew.-%, meist ≥ 0,05 Gew.-%).Due to numerous occurring in the course of the catalytic gas phase oxidation Parallel and follow-up reactions as well as due to the inert to be used However, the dilution phase is not a pure one in catalytic gas phase oxidation (Meth) acrylic acid, but obtained a reaction mixture that essentially (Meth) acrylic acid, which contains inert diluent gases and by-products, from which the (meth) acrylic acid must be separated. In addition to (meth) acrylic acid comparatively easy to remove and for subsequent uses of (meth) acrylic acid the reaction gas mixture contains less disruptive by-products such as acetic acid often also closely related to (meth) acrylic acid and therefore difficult for (meth) acrylic acid separable lower aldehydes such as formaldehyde, acetaldehyde, acrolein, methacrolein, Propionaldehyde, n-butyraldehyde, benzaldehyde, furfural and crotonaldehyde as well additionally optionally maleic anhydride (based on that in the reaction gas mixture Containing amount of (meth) acrylic acid is the total amount of this, at Subsequent uses often significantly disruptive, secondary components usually ≤ 2 % By weight, usually ≥ 0.05% by weight).

    Es ist außerdem praktikabel, Acrylsäure aus dem Reaktionsgasgemisch der katalytischen Gasphasenoxidation von Propylen und/oder Acrolein durch Gegenstromadsorption mit einer hochsiedenden inerten hydrophoben organischen Flüssigkeit abzutrennen. Die Inhibitorkomposition kann dabei direkt in den Gasstrom bzw. in die Vorrichtung zur Gegenstromadsorption eingespritzt werden. Als organische Flüssigkeit für die Gegenstromadsorption kommen dabei u.a. höhere Alkohole oder Ester dieser (insbesondere solche mit (Meth)acrylsäure), in Frage. Das Verfahren wird im wesentlichen so durchgeführt, daß man das Reaktionsgasgemisch in einer konventionellen Adsorptionskolonne zu der absteigenden Adsorptionsflüssigkeit im Gegenstrom führt, danach in einer Desorptionskolonne aus dem im wesentlichen aus Acrylsäure, dem Adsorptionsmittel und Nebenkomponenten zusammmengesetzten Flüssigkeitsablauf der Adsorptionskolonne durch Strippen (Abstreifen) mit Inertgas die einfach abtrennbaren leichtflüchtigen Nebenkomponenten weitgehend entfernt und anschließend den (Meth)acrylsäure und das Adsorbens als Hauptbestandteile enthaltenden Flüssigkeitsablauf der Desorptionskolonne zur Abtrennung von Roh-Acrylsäure rektifikativ behandelt.It is also practical to use acrylic acid from the reaction gas mixture of the catalytic Gas phase oxidation of propylene and / or acrolein by countercurrent adsorption a high-boiling inert hydrophobic organic liquid. The Inhibitor composition can be directly in the gas stream or in the device for Countercurrent adsorption are injected. As an organic liquid for the Counterflow adsorption comes, among other things, higher alcohols or esters of these (especially those with (meth) acrylic acid) in question. The procedure is essentially performed so that the reaction gas mixture in a conventional Adsorption column leads to the descending adsorption liquid in countercurrent, then in a desorption column from essentially acrylic acid, the Adsorbent and secondary components compound liquid drain Adsorption column by stripping (stripping) with inert gas, the easily separable volatile secondary components largely removed and then the (Meth) acrylic acid and the liquid drain containing the adsorbent as main components the desorption column for the separation of crude acrylic acid treated rectificatively.

    Das Problem einer rektifikativen Abtrennung von (Meth)acrylsäure erwächst auch dann, wenn man die (Meth)acrylsäure aus den Reaktionsgasen der katalytischen Gasphasenoxidation zunächst in Wasser aufnimmt und anschließend unter Zusatz eines organischen azeotropen Schleppers aus den wäßrigen (Meth)acrylsäure enthaltenden Gemischen das Wasser rektifikativ abtrennt.The problem of a rectificative separation of (meth) acrylic acid also arises if you take the (meth) acrylic acid from the reaction gases of the catalytic Gas phase oxidation first takes up in water and then with the addition of a organic azeotropic tractor from the aqueous (meth) acrylic acid-containing Mixes the water by rectification.

    Das Problem besteht aber auch bei der rektifikativen Herstellung von Reinacrylsäure (Reinheit > 99,7 Gew. -%) aus Roh-Acrylsäure (Reinheit > 99 Gew. -%).The problem also exists in the rectificative production of pure acrylic acid (Purity> 99.7% by weight) from crude acrylic acid (purity> 99% by weight).

    Bei allen diesen vorgenannten Rektifikationsproblemen ist die erfindungsgemäße Inhibitorkomposition anwendbar. Selbstverständlich kann die erfindungsgemäße Inhibitorkomposition auch bei der Extraktion der (Meth)acrylsäure aus dem Reaktionsgemisch der Gasphasenoxidation eingesetzt werden. Die Inhibitorkomposition kann dabei direkt in den Gasstrom eingespritzt werden. Die Stabilisierung empfiehlt sich auch für den Fall einer kristallisativen Abtrennung von (Meth)acrylsäure oder deren Ester enthaltenden Gemischen.In all of these rectification problems mentioned above, the invention is Inhibitor composition applicable. Of course, the invention Inhibitor composition also in the extraction of (meth) acrylic acid from the Reaction mixture of the gas phase oxidation can be used. The inhibitor composition can be injected directly into the gas stream. Stabilization is recommended also in the case of a crystallized separation of (meth) acrylic acid or its ester containing mixtures.

    (Meth)acrolein ist in entsprechender Weise wie (Meth)acrylsäure z.B. durch katalytische Gasphasenoxidation erhältlich. Allerdings wird die Oxidation nach der ersten Oxidationsstufe nicht weitergeführt. Vielmehr wird das im Reaktionsgasgemisch enthaltende (Meth)acrolein in der Regel zunächst mittels Wasser extraktiv aus dem Reaktionsgasgemisch abgetrennt und anschließend destillativ (rektifikativ) aus der wäßrigen Lösung gewonnen. Für alle genannten Prozeßschritte eignet sich zur Stabilisation die erfindungsgemäße Inhibitorkomposition.(Meth) acrolein is similar to (meth) acrylic acid e.g. through catalytic Gas phase oxidation available. However, the oxidation occurs after the first Oxidation level discontinued. Rather, it is in the reaction gas mixture Containing (meth) acrolein usually first extractively from the water Separated reaction gas mixture and then by distillation (rectification) from the aqueous solution. Stabilization is suitable for all the process steps mentioned the inhibitor composition according to the invention.

    Die synergistische Wirksamkeit der erfindungsgemäßen Inhibitorkomposition gilt im wesentlichen unabhängig vom pH-Wert und sowohl für niedere (z.B. Raumtemperatur) als auch für erhöhte Temperaturen, wie sie z. B. im Rahmen von thermischen physikalischen Trennverfahren als auch für bei erhöhten Temperaturen ablaufende chemische Umsetzungen üblich sind.The synergistic effectiveness of the inhibitor composition according to the invention applies in essentially independent of the pH value and both for lower (e.g. room temperature) than also for elevated temperatures, as z. B. in the context of thermal physical Separation processes as well as for chemical processes occurring at elevated temperatures Implementations are common.

    Insbesondere gilt das vorgenannte für eine Stabilisierung von (Meth)acrylsäure und/oder deren Ester, deren ethylenisch ungesättigte Doppelverbindung bezüglich einer radikalischen Polymerisation besonders aktiv ist.In particular, the above applies to the stabilization of (meth) acrylic acid and / or their esters, their ethylenically unsaturated double compound with respect to a radical polymerization is particularly active.

    In der Regel wird die Inhibitorkomposition so gewählt, daß die in der Inhibitorkomposition enthaltenen Komponenten in der zu stabilisierenden Substanz in ihrer Einsatzmenge in vollem Umfang löslich sind. Häufig erfolgt ihre Zugabe nicht als Reinsubstanz, sondern als Suspension, Emulsion oder Lösung. Als Lösungs- und/oder Dispergiermedium kommen insbesondere diejenigen Substanzen in Betracht, die Bestandteil des zu stabilisierenden Systems sind, d.h., z.B. bei chemischen Umsetzungen wie Veresterungen alle Edukte und Produkte.
    Im folgenden soll die Erfindung anhand eines Ausführungsbeispiels näher erläutert werden.    As a rule, the inhibitor composition is chosen such that the amount of the components contained in the inhibitor composition is completely soluble in the substance to be stabilized. Often they are not added as pure substance, but as a suspension, emulsion or solution. Suitable solvents and / or dispersing media are, in particular, those substances which are part of the system to be stabilized, ie, for example in chemical reactions such as esterifications, all starting materials and products.
    In the following, the invention will be explained in more detail using an exemplary embodiment.

    Beispiel:Example:

    1ml Acrylsäure wurde jeweils mit verschiedenen Stabilisatoren unterschiedlicher Menge versetzt und in Glasampullen (Innenvolumen 1,9 ml) unter Luft gasdicht eingeschlossen. Die Ampullen wurden vollständig in ein 120°C heißes Ölbad eingetaucht und unter Lichtausschluß gelagert. 1ml acrylic acid was used with different stabilizers of different amounts added and enclosed gas-tight in glass ampoules (inner volume 1.9 ml) in air. The vials were completely immersed in a 120 ° C oil bath and under Light exclusion stored.

    Anschließend wurde die Zeit bestimmt, bis die Acrylsäure auspolymerisiert war. Dabei wurde visuell der Zeitpunkt ermittelt, bei dem man die Verfestigung der Polymerisationsmischung erkennen konnte. Die nachstehende Tabelle zeigt die zugesetzten Mengen der Komponenten des Inhibitors und entsprechend die Zeit bis zum Festwerden der entsprechenden Polymerisationsmischung. Versuchs-Nr. HO-TEMPO (ppm) H3PO3 ppm MEHQ ppm Zeit (min) 1 10 77 2 25 16,5 3 50 55 4 25 50 71,5 5 10 25 110 6 10 50 214 7 10 25 50 319 Angaben jeweils in Gew.-ppm bezogen auf die zugesetzte Acrylsäure
    HO-Tempo: 4-Hydroxy-1-oxyl-2,2,6,6-tetramethylpiperidin
    MEHQ: Hydrochinonmonomethylether         The time was then determined until the acrylic acid had polymerized. The point in time at which the solidification of the polymerization mixture could be seen was determined visually. The table below shows the added amounts of the components of the inhibitor and correspondingly the time until the corresponding polymerization mixture has solidified. Experiment no. HO-TEMPO (ppm) H 3 PO 3 ppm MEHQ ppm Time (min) 1 10 77 2 25th 16.5 3rd 50 55 4th 25th 50 71.5 5 10 25th 110 6 10 50 214 7 10 25th 50 319 Figures in ppm by weight based on the added acrylic acid
    HO tempo: 4-hydroxy-1-oxyl-2,2,6,6-tetramethylpiperidine
    MEHQ: hydroquinone monomethyl ether

    Die Versuchsergebnisse zeigen, daß bei Verwendung aller drei Inhibitortypen - also Verbindungen, die ein Phosphoratom in der Oxidationszahl +3 aufweisen, sowie Nitroxyl-Radikal(derivate) und Phenol(derivate) - eine besonders lange Zeit bis zum Festwerden der entsprechenden Probe zu verzeichnen ist. Das zeigt, daß die synergistische Wirkung (die gegenseitige Steigerung der inhibierenden Wirkung der einzelnen Komponenten) dieser Dreierkomposition" besonders intensiv ist.The test results show that when all three inhibitor types are used - that is to say compounds which have a phosphorus atom in the oxidation number +3, and nitroxyl radical (derivatives) and phenol (derivatives) - there is a particularly long time before the corresponding sample has solidified . This shows that the synergistic effect (the mutual increase in the inhibitory effect of the individual components) of this Triple composition "is particularly intense.

    Claims (7)

    Inhibitorkomposition enthaltend als Komponenten a) wenigstens ein Nitroxyl-Radikal(derivat), b) wenigstens ein Phenol(derivat) und c) wenigstens eine weitere chemische Verbindung, welche mindestens ein Phosphoratom enthält, das die Oxidationszahl +3 aufweist.Inhibitor composition containing as components a) at least one nitroxyl radical (derivative), b) at least one phenol (derivative) and c) at least one further chemical compound which contains at least one phosphorus atom, which Has oxidation number +3. Inhibitorkomposition nach Anspruch 1, dadurch gekennzeichnet, daß als Nitroxyl-Radikal(derivat) 4-Hydroxy-1-oxyl-2,2,6,6-tetramethylpiperidin eingesetzt wird.Inhibitor composition according to Claim 1, characterized in that the nitroxyl radical (derivative) 4-hydroxy-1-oxyl-2,2,6,6-tetramethylpiperidine is used. Inhibitorkomposition nach Anspruch 1 oder 2, dadurch gekennzeichnet, daß als Verbindung, die mindestens ein Phosphoratom enthält, Orthophosphorige Säure oder ein Ester der Orthophosphorigen Säure eingesetzt wird.Inhibitor composition according to claim 1 or 2, characterized in that as Compound containing at least one phosphorus atom, orthophosphorous acid or an ester of orthophosphorous acid is used. Inhibitorkomposition nach einem der Ansprüche 1 bis 3, dadurch gekennzeichnet, daß als Phenol(derivat) ein Phenol oder Kresol, bei dem ein oder mehrere Wasserstoffatome durch tert.-Butyl-Gruppen substituiert sind, insbesondere 2,6-Di-tert.-butylkresol oder Hydrochinone, insbesondere Hydrochinonmonomethylether, eingesetzt wird.Inhibitor composition according to one of claims 1 to 3, characterized in that as a phenol (derivative) a phenol or cresol in which one or more Hydrogen atoms are substituted by tert-butyl groups, in particular 2,6-di-tert-butyl cresol or hydroquinones, especially hydroquinone monomethyl ether, is used. Gemisch enthaltend wenigstens eine Verbindung, die mindestens eine vinylisch ungesättigte Gruppe aufweist und eine Inhibitorkomposition gemäß einem der Ansprüche 1 bis 4. Mixture containing at least one compound which is at least one vinyl has unsaturated group and an inhibitor composition according to one of the Claims 1 to 4. Gemisch nach Anspruch 5 enthaltend als Inhibitorkomposition ein oder mehrere chemische Verbindungen, welche mindestens ein die Oxidationszahl +3 aufweisendes Phosphoratom enthalten, in einer Gesamtkonzentration von 1 bis 5000 ppm, bevorzugt von 5 bis 1000 ppm, sowie ein oder mehrere Nitroxyl-Radikal(derivate) in einer Gesamtkonzentration von 1 bis 3000 ppm, bevorzugt von 5 bis 300 ppm und ein oder mehrere Phenolderivate in einer Gesamtkonzentration von 1 bis 3000 ppm, bevorzugt von 5 bis 1500 ppm.Mixture according to Claim 5, comprising one or more as inhibitor composition chemical compounds which have at least one oxidation number +3 Contain phosphorus atom, in a total concentration of 1 to 5000 ppm, preferred from 5 to 1000 ppm, as well as one or more nitroxyl radicals (derivatives) in one Total concentration from 1 to 3000 ppm, preferably from 5 to 300 ppm and one or several phenol derivatives in a total concentration of 1 to 3000 ppm, preferred from 5 to 1500 ppm. Verwendung von Inhibitorkompositionen gemäß einem der Ansprüche 1 bis 4 zur Stabilisierung von Reinsubstanzen, die mindestens eine vinylisch ungesättigte Gruppe aufweisen oder von Gemischen, die wenigstens eine Substanz enthalten, welche mindestens eine vinylisch ungesättigte Gruppe aufweist.Use of inhibitor compositions according to one of claims 1 to 4 for Stabilization of pure substances that have at least one vinylically unsaturated group have or of mixtures containing at least one substance which has at least one vinylically unsaturated group.
    EP00116293A 1999-08-17 2000-08-10 Inhibitor composition for stabilising radically polymerisable substances Expired - Lifetime EP1077245B1 (en)

    Applications Claiming Priority (2)

    Application Number Priority Date Filing Date Title
    DE19938841A DE19938841A1 (en) 1999-08-17 1999-08-17 Inhibitor composition for the stabilization of radical polymerisable substances
    DE19938841 1999-08-17

    Publications (3)

    Publication Number Publication Date
    EP1077245A2 true EP1077245A2 (en) 2001-02-21
    EP1077245A3 EP1077245A3 (en) 2001-03-07
    EP1077245B1 EP1077245B1 (en) 2004-01-07

    Family

    ID=7918581

    Family Applications (1)

    Application Number Title Priority Date Filing Date
    EP00116293A Expired - Lifetime EP1077245B1 (en) 1999-08-17 2000-08-10 Inhibitor composition for stabilising radically polymerisable substances

    Country Status (6)

    Country Link
    US (2) US6458956B1 (en)
    EP (1) EP1077245B1 (en)
    JP (1) JP2001081461A (en)
    KR (1) KR100692225B1 (en)
    CA (1) CA2314875C (en)
    DE (2) DE19938841A1 (en)

    Cited By (2)

    * Cited by examiner, † Cited by third party
    Publication number Priority date Publication date Assignee Title
    EP1232212B1 (en) * 1999-11-25 2006-05-10 Ciba SC Holding AG Composition and method for color improvement of nitroxyl containing polymers
    DE112005001915B4 (en) * 2004-08-05 2017-03-02 Basf Se Stabilizers for NVP synthesis

    Families Citing this family (28)

    * Cited by examiner, † Cited by third party
    Publication number Priority date Publication date Assignee Title
    DE19938841A1 (en) * 1999-08-17 2001-02-22 Basf Ag Inhibitor composition for the stabilization of radical polymerisable substances
    US6685823B2 (en) * 2000-10-16 2004-02-03 Uniroyal Chemical Company, Inc. C-nitrosoaniline compounds and their blends as polymerization inhibitors
    DE10122787A1 (en) 2001-05-10 2002-06-06 Basf Ag Preparation of purified melt of monomer(s) involves forming gaseous or liquid monomer-containing phase, condensing, absorbing or extracting from raw melt and crystallizing
    DE10122788A1 (en) 2001-05-10 2002-06-06 Basf Ag Preparation of purified melt of monomer(s) involves forming suspension, crystallizing, mechanically separating suspended monomer crystals and further crystallizing and separating
    AU2003246862A1 (en) * 2002-04-29 2003-11-17 Rhodia Chimie Assembly for hydrosylilation, method for preparing same and silicone compositions incorporating same
    DE102004058071A1 (en) * 2004-12-01 2006-06-08 Basf Ag Process for the purification of polar vinyl compounds
    DE102006008998A1 (en) * 2006-02-23 2007-08-30 Röhm Gmbh Stabiliser mixture, especially for the production of alkoxypolyoxyalkylene (meth)acrylate, comprises a hydroquinone mono-ether, a phenolic antioxidant and a 2,2,6,6-tetra-substituted hydroxypiperidine derivative
    US7968001B2 (en) 2007-12-19 2011-06-28 Air Products And Chemicals, Inc. Stabilizers for the stabilization of unsaturated hydrocarbon-based precursor
    US8440099B2 (en) * 2007-12-19 2013-05-14 Air Products And Chemicals, Inc. Stabilizers for the stabilization of unsaturated hydrocarbon-based precursor
    CN101591216B (en) * 2009-07-10 2012-07-04 北京斯伯乐科学技术研究院 High-efficiency multi-functional polymerization inhibitor for butadiene extraction device and using method thereof
    EP2325214B1 (en) 2009-11-20 2015-11-18 King Saud University Synthesis of acrylic or methacrylic acid/acrylate or methacrylate ester polymers using pervaporation
    US10351689B2 (en) 2014-08-22 2019-07-16 Arkema Inc. Voided latex particles
    CN107001724B (en) * 2014-12-09 2019-11-19 阿科玛股份有限公司 The peroxide of liquid and the protection of the incipient scorch of fusible solid grade
    GB2544272B (en) * 2015-11-06 2020-02-19 Henkel IP & Holding GmbH Cyanoacrylate compositions
    US20170327454A1 (en) 2016-05-13 2017-11-16 Sirrus, Inc. High purity 1,1-dicarbonyl substituted-1-alkenes and methods for their preparation
    US9567475B1 (en) 2016-06-03 2017-02-14 Sirrus, Inc. Coatings containing polyester macromers containing 1,1-dicarbonyl-substituted 1 alkenes
    JP2020534353A (en) 2017-09-19 2020-11-26 シラス・インコーポレイテッド Catalytic cycle for the production of 1,1-disubstituted alkenes
    WO2019108680A1 (en) 2017-11-29 2019-06-06 Sirrus, Inc. Initiated chemical vapor deposition of 1,1 disubstituted alkene compounds
    WO2019125930A1 (en) 2017-12-18 2019-06-27 Sirrus, Inc. Methylene malonamide and ketoacrylamide monomers and polymeric compositions derived from them
    US20210032387A1 (en) 2018-01-12 2021-02-04 Sirrus, Inc. Emulsion polymers crosslinked with compounds containing two or more dicarbonyl-substituted 1 alkene units
    WO2019195366A1 (en) 2018-04-03 2019-10-10 Sirrus, Inc. Heterogeneous catalytic transesterification of ester compounds with groups reactive under transesterification conditions
    WO2020123581A1 (en) 2018-12-11 2020-06-18 Sirrus, Inc. Emulsion polymers of 1,1-dicarbonyl 1-alkenes of controlled particle size
    WO2020123579A1 (en) 2018-12-11 2020-06-18 Sirrus, Inc. Polymerization of 1,1-dicarbonyl 1-alkenes
    WO2020131745A1 (en) 2018-12-17 2020-06-25 Sirrus, Inc. Surface initiated polymerization of compositions having 1,1-disubstituted alkene compounds
    WO2020167621A1 (en) 2019-02-14 2020-08-20 Sirrus, Inc. Particles encapsulated with dicarbonyl-substituted-1- alkenes
    WO2021150844A1 (en) 2020-01-24 2021-07-29 Sirrus, Inc. Compositions containing 1,1-disubstituted activated alkenes useful in additive manufacturing and articles formed therefrom
    WO2021183340A1 (en) 2020-03-10 2021-09-16 Sirrus, Inc. Radiation cured copolymers of dicarbonyl substituted-l-alkenes and electron rich comonomers
    WO2021231288A1 (en) 2020-05-15 2021-11-18 Nippon Shokubai Co., Ltd. Improved dicarbonyl substituted-1-alkene compositions

    Citations (5)

    * Cited by examiner, † Cited by third party
    Publication number Priority date Publication date Assignee Title
    US3818079A (en) * 1970-07-07 1974-06-18 Japanese Geon Co Ltd Method of preventing the polymerization of unsaturated carboxylic acid
    US5322960A (en) * 1993-04-15 1994-06-21 Nippon Shokubai Co., Ltd. Method for inhibiting polymerization of (meth) acrylic acid and esters thereof
    DE19651307A1 (en) * 1996-12-10 1998-06-18 Basf Ag Mixtures of compounds containing vinyl group-containing compounds and stabilizers
    DE19707151A1 (en) * 1997-02-22 1998-08-27 Merck Patent Gmbh Calorimetric liquid containing stabiliser to prevent colour fading in daylight
    WO2000036052A1 (en) * 1998-12-17 2000-06-22 Nalco/Exxon Energy Chemicals, L.P. Inhibiting polymerization of vinyl aromatic monomers using synergistic mixtures containing nitroxide stabilizers

    Family Cites Families (4)

    * Cited by examiner, † Cited by third party
    Publication number Priority date Publication date Assignee Title
    US4187382A (en) 1976-12-28 1980-02-05 Union Carbide Corporation Process for producing low color residue acrylate ester monomers
    DE2913218A1 (en) 1979-04-03 1980-10-23 Bayer Ag Prepn. of (meth)acrylic acid ester(s) - by esterification of (meth)acrylic acid with poly:hydric alcohol(s) in presence of phosphite ester and a phenol
    US5844025A (en) * 1996-12-02 1998-12-01 Ciba Specialty Chemicals Corporation 1,2-Bis-adducts of stable nitroxides with substituted ethylenes and stabilized compositions
    DE19938841A1 (en) * 1999-08-17 2001-02-22 Basf Ag Inhibitor composition for the stabilization of radical polymerisable substances

    Patent Citations (6)

    * Cited by examiner, † Cited by third party
    Publication number Priority date Publication date Assignee Title
    US3818079A (en) * 1970-07-07 1974-06-18 Japanese Geon Co Ltd Method of preventing the polymerization of unsaturated carboxylic acid
    US5322960A (en) * 1993-04-15 1994-06-21 Nippon Shokubai Co., Ltd. Method for inhibiting polymerization of (meth) acrylic acid and esters thereof
    EP0620206A1 (en) * 1993-04-15 1994-10-19 Nippon Shokubai Co., Ltd. Method for inhibiting polymerization of (meth)acrylic acid and esters thereof
    DE19651307A1 (en) * 1996-12-10 1998-06-18 Basf Ag Mixtures of compounds containing vinyl group-containing compounds and stabilizers
    DE19707151A1 (en) * 1997-02-22 1998-08-27 Merck Patent Gmbh Calorimetric liquid containing stabiliser to prevent colour fading in daylight
    WO2000036052A1 (en) * 1998-12-17 2000-06-22 Nalco/Exxon Energy Chemicals, L.P. Inhibiting polymerization of vinyl aromatic monomers using synergistic mixtures containing nitroxide stabilizers

    Cited By (2)

    * Cited by examiner, † Cited by third party
    Publication number Priority date Publication date Assignee Title
    EP1232212B1 (en) * 1999-11-25 2006-05-10 Ciba SC Holding AG Composition and method for color improvement of nitroxyl containing polymers
    DE112005001915B4 (en) * 2004-08-05 2017-03-02 Basf Se Stabilizers for NVP synthesis

    Also Published As

    Publication number Publication date
    CA2314875A1 (en) 2001-02-17
    DE50004965D1 (en) 2004-02-12
    CA2314875C (en) 2007-06-19
    US20030097017A1 (en) 2003-05-22
    JP2001081461A (en) 2001-03-27
    US6458956B1 (en) 2002-10-01
    EP1077245A3 (en) 2001-03-07
    KR20010039816A (en) 2001-05-15
    KR100692225B1 (en) 2007-03-09
    EP1077245B1 (en) 2004-01-07
    US6726854B2 (en) 2004-04-27
    DE19938841A1 (en) 2001-02-22

    Similar Documents

    Publication Publication Date Title
    EP1077245B1 (en) Inhibitor composition for stabilising radically polymerisable substances
    DE60036018T2 (en) COMPOSITIONS AND METHODS OF INHIBITING POLYMERIZATION AND POLYMER GROWTH
    DE19956509A1 (en) Inhibitor composition for (meth)acrylic acid stabilization comprises nitroxyl radical(s) (derivative) and a phenothiazine(s) and/or phenothiazine derivative(s)
    DE60116894T2 (en) C-NITROSOANILINE COMPOUNDS AND THEIR MIXTURES AS POLYMERIZATION INHIBITORS
    DE60037140T2 (en) POLYMERIZATION INHIBITION OF UNSATURATED MONOMERS
    EP1834941A2 (en) Polymerisation inhibitor for stabilizing olefinically unsaturated monomers
    EP1144353B1 (en) Method for stabilizing chemical compounds containing at least one ethylenically unsaturated bond in order to prevent undesirable radical polymerization
    DE60023735T2 (en) PREVENTING THE POLYMERIZATION OF UNSATURATED MOMOMERS
    EP0885180B1 (en) Stabilized monomer composition
    EP1056711B1 (en) Process for stabilising (metha)acrylic esters against unwanted radical polymerisation
    DE102008061611A1 (en) Stabilizing water-aromatic solvent mixtures, e.g. quenching mixtures from acetylene production, by adding N-oxyl, aromatic or aliphatic amine or phenol as polymerization inhibitor
    DE69724432T2 (en) polymerization inhibitor
    DE60105890T2 (en) Process for inhibiting the polymerization of unsaturated monomers and their preparation
    DE69912203T2 (en) METHOD FOR INHIBITING THE POLYMERIZATION OF VINYL COMPOUNDS
    WO2000076943A1 (en) Method for preventing undesired polymerisation in a mixture of substances containing ethylenically unsaturated compounds
    WO2000055279A1 (en) Inhibitor composition for stabilising radically polymerisable substances
    EP1086939A1 (en) Inhibitor composition
    DE60127188T2 (en) RECOVERY OF NITROXYL-CONTAINING FLOWS AT LOW TEMPERATURE
    DE19734171A1 (en) (Meth)acrylic acid ester(s) with improved inhibition efficiency
    DE10139767A1 (en) Stabilization of ethylenically unsaturated compounds with amidoximes
    EP1154974B1 (en) Method for the continuous recovery of styrene from a mixture containing same
    DE19915165A1 (en) Inhibitor composition, useful to inhibit the polymerization of radically polymerizable mixtures comprises a polyvinylimidazole and a phenothiazine
    DE19954582A1 (en) Stabilization of radically polymerizable ethylenically unsaturated monomer(s) comprises adding solution of stable N-oxy radical(s) in inert solvent
    DE19922103A1 (en) Inhibiting polymerisation of vinyl monomers using composition containing nitroxyl compound, a preferably aromatic nitro compound as retarder, oxygen and optionally transition metal compound and co-stabilizer
    WO2001025173A1 (en) Treatment of mixtures that contain at least one compound with at least one ethylenically unsaturated group

    Legal Events

    Date Code Title Description
    PUAI Public reference made under article 153(3) epc to a published international application that has entered the european phase

    Free format text: ORIGINAL CODE: 0009012

    PUAL Search report despatched

    Free format text: ORIGINAL CODE: 0009013

    AK Designated contracting states

    Kind code of ref document: A2

    Designated state(s): BE DE FR IT NL

    AX Request for extension of the european patent

    Free format text: AL;LT;LV;MK;RO;SI

    AK Designated contracting states

    Kind code of ref document: A3

    Designated state(s): AT BE CH CY DE DK ES FI FR GB GR IE IT LI LU MC NL PT SE

    AX Request for extension of the european patent

    Free format text: AL;LT;LV;MK;RO;SI

    17P Request for examination filed

    Effective date: 20010711

    AKX Designation fees paid

    Free format text: BE DE FR IT NL

    GRAH Despatch of communication of intention to grant a patent

    Free format text: ORIGINAL CODE: EPIDOS IGRA

    GRAS Grant fee paid

    Free format text: ORIGINAL CODE: EPIDOSNIGR3

    GRAA (expected) grant

    Free format text: ORIGINAL CODE: 0009210

    AK Designated contracting states

    Kind code of ref document: B1

    Designated state(s): BE DE FR IT NL

    REF Corresponds to:

    Ref document number: 50004965

    Country of ref document: DE

    Date of ref document: 20040212

    Kind code of ref document: P

    ET Fr: translation filed
    PLBE No opposition filed within time limit

    Free format text: ORIGINAL CODE: 0009261

    STAA Information on the status of an ep patent application or granted ep patent

    Free format text: STATUS: NO OPPOSITION FILED WITHIN TIME LIMIT

    26N No opposition filed

    Effective date: 20041008

    PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

    Ref country code: DE

    Payment date: 20070802

    Year of fee payment: 8

    PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

    Ref country code: IT

    Payment date: 20070830

    Year of fee payment: 8

    Ref country code: NL

    Payment date: 20070805

    Year of fee payment: 8

    PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

    Ref country code: BE

    Payment date: 20071018

    Year of fee payment: 8

    PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

    Ref country code: FR

    Payment date: 20070808

    Year of fee payment: 8

    NLV4 Nl: lapsed or anulled due to non-payment of the annual fee

    Effective date: 20090301

    PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

    Ref country code: NL

    Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

    Effective date: 20090301

    REG Reference to a national code

    Ref country code: FR

    Ref legal event code: ST

    Effective date: 20090430

    PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

    Ref country code: BE

    Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

    Effective date: 20080831

    PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

    Ref country code: IT

    Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

    Effective date: 20080810

    Ref country code: DE

    Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

    Effective date: 20090303

    Ref country code: FR

    Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

    Effective date: 20080901